CN113307971B - Polyimide precursor and application thereof - Google Patents

Polyimide precursor and application thereof Download PDF

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CN113307971B
CN113307971B CN202010121146.7A CN202010121146A CN113307971B CN 113307971 B CN113307971 B CN 113307971B CN 202010121146 A CN202010121146 A CN 202010121146A CN 113307971 B CN113307971 B CN 113307971B
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polyimide
diamine monomer
baking
polyimide precursor
flexible copper
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CN113307971A (en
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梁立
茹敬宏
伍宏奎
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Shengyi Technology Co Ltd
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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
    • 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
    • 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
    • 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
    • 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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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The invention relates to a polyimide precursor and application thereof, wherein the preparation raw materials of the polyimide precursor comprise diamine monomers and dianhydride monomers; the diamine monomer comprises 2- (diaminophenyl) benzimidazole-5 amine (BIA) and diamine monomer A, wherein the mass ratio of the 2- (diaminophenyl) benzimidazole-5 amine to the diamine monomer A is (1-4): 1; according to the invention, BIA is firstly introduced into polyimide precursor raw materials, the polyimide synthesized by BIA has very low CTE, and because imidazole can form a complex with copper foil, good peel strength is maintained; meanwhile, diamine monomer A containing small side groups is introduced to be matched with BIA, so that the final polyimide can keep low CTE, and the precursor polyamic acid of the final polyimide can keep larger CTE, so that shrinkage of an adhesive layer in a coating heating process is reduced, the problem that the coating processing process is easy to turn over is solved, and the peeling strength of the flexible copper-clad plate is improved.

Description

Polyimide precursor and application thereof
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 such as notebook computers, mobile phones, personal digital assistants, and digital cameras, and as the technical requirements of the electronics industry are increasing, consumer electronics are rapidly moving to thin, light, short, and small, and increasingly require a corresponding flexible copper-clad plate to be lighter, thinner, and have high heat resistance and high reliability. The adhesive-free flexible copper-clad plate has been rapidly developed in recent years due to the adoption of polyimide resin which is excellent in mechanical properties, electrical properties and heat resistance.
The preparation method of the glue-free flexible copper-clad plate comprises a pressing method and a coating method, wherein the pressing method adopts a high-temperature roll squeezer to roll the Thermoplastic Polyimide (TPI) composite film and the copper foil at high temperature to prepare the glue-free flexible copper-clad plate, and the production process is relatively simple and easy to realize; compared with a lamination method, the coating method flexible copper-clad plate can be used for preparing the glue-free flexible copper-clad plate with more excellent mechanical property and dimension expansion and contraction due to the fact that the polyimide formula can be regulated and controlled. At present, no matter how to cope with the requirement of a Chip On Film (COF) on the low Coefficient of Thermal Expansion (CTE) of a glue-free flexible copper-clad plate or how to pursue better dimensional stability of the glue-free flexible copper-clad plate, the polyimide layer of the glue-free flexible copper-clad plate is required to have lower CTE. For coating-method glue-free flexible copper clad laminates, low CTE, high peel strength and good processability are a group of contradictions that are not easily resolved. Lowering the CTE of the polyimide, the bonding force with the copper foil is lowered; the CTE of polyimide is reduced, and the CTE of a precursor polyamide acid is also lower, so that the glue layer is seriously contracted in the temperature rising stage, and the glue-free flexible copper-clad plate is easy to turn over during coating.
CN107266683a discloses a thermoplastic polyimide film and a glue-free flexible copper-clad plate prepared from the same. The method overcomes the mutual restriction relation between the thermoplasticity of the Polyimide (PI) film and the high Tg and the thermoplasticity and the low CTE of the Polyimide (PI) film, and the prepared PI film has excellent comprehensive properties including good thermoplasticity, high Tg, low CTE and good bonding strength with copper foil. However, the polyimide precursor used in the present invention has a low CTE and is liable to be folded during coating.
CN102993748A discloses a TPI film with low thermal expansion coefficient and a preparation method thereof, and a method for preparing two-layer flexible copper-clad plate by using the TPI film. When the thermoplastic polyimide film is prepared, a certain molar ratio of di (4-aminobenzene) -4- (tribromomethyl) phenyl phosphine oxide and 3-phenyl-2, 6-di (4-aminophenyl) pyridine are firstly utilized to carry out solution polymerization by combining corresponding diamine and dianhydride to generate a polyamic acid copolymer, the solvent is removed by drying, and the copolymer is treated by a thermal imidization method to obtain the TPI film with excellent hot melting performance and dimensional stability. After the TPI film is compounded with the thermosetting polyimide film and the copper foil under certain pressure and temperature, the two-layer flexible copper-clad plate material with good comprehensive properties such as stripping performance, dip soldering resistance, dimensional stability and the like can be obtained. But the bonding property of the TPI film with lower CTE and the copper foil is poor, the peel strength of the obtained copper-clad plate is lower, and the copper-clad plate is easy to turn over in the polyimide precursor coating process.
Therefore, the development of a novel polyimide precursor is needed in the field, the adhesive-free flexible copper-clad plate with smaller polyimide CTE can be prepared, good peel strength is maintained, and the turnover phenomenon can not occur in the coating processing process.
Disclosure of Invention
The invention aims to provide a polyimide precursor, in particular to a polyimide precursor applied to a flexible copper-clad plate, which can be used for preparing a glue-free flexible copper-clad plate with smaller polyimide CTE, keeps good peel strength and can not generate a turnover phenomenon in the coating processing process.
To achieve the purpose, the invention adopts the following technical scheme:
the invention provides a polyimide precursor, wherein the preparation raw materials of the polyimide precursor comprise diamine monomers and dianhydride monomers;
the diamine monomer comprises 2- (diaminophenyl) benzimidazole-5 amine and diamine monomer A;
Figure BDA0002393005650000031
the R is 1 ～R 8 Each independently selected from-H, -F, -CH 3 or-CF 3 Provided that R 1 ～R 4 At least one of them is selected from-CH 3 or-CF 3 And R is 5 ～R 8 At least one of them is selected from-CH 3 or-CF 3 ；
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, etc.).
According to the invention, BIA is firstly introduced into a polyimide precursor raw material formula, the polyimide synthesized by BIA has very low CTE, and because imidazole can form a complex with copper foil, good peel strength is maintained; meanwhile, a diamine monomer A containing a small side group is introduced into a raw material formula of the polyimide precursor, and the diamine monomer A is matched with BIA, so that the final polyimide can keep a very low CTE, and the precursor polyamic acid can keep a relatively large CTE, the shrinkage of a glue layer in the coating heating process is reduced, the problem that the coating processing process is easy to fold is solved, and the peeling strength of the flexible copper clad laminate is improved.
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 properties of polyimide CTE, coating warp degree and peeling strength of the flexible copper clad laminate, controls CTE below 10 ppm/DEG C, and the coating warp height to be 3.2-4.8 cm, and the peeling strength of the flexible copper clad laminate to be 1.25-1.38N/mm. Too high BIA content may lead to a deterioration in warpage, and may cause brittleness of polyimide, adversely affecting peel strength, and too high diamine monomer A content may lead to an increase in CTE value.
Preferably, the sum of the masses of the 2- (diaminophenyl) benzimidazole-5 amine and the diamine monomer a is 30 to 95%, 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., of the total mass of the diamine monomer.
Preferably, the diamine monomer a includes 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.
The second object of the present invention is to provide a polyimide precursor glue solution, wherein the polyimide precursor glue solution comprises the polyimide precursor and a solvent.
Preferably, the solvent comprises N-methylpyrrolidone and/or N, N' -dimethylacetamide.
Preferably, the viscosity of the polyimide precursor solution is 15000-25000 cp, for example 16000cp, 17000cp, 18000cp, 19000cp, 20000cp, 21000cp, 22000cp, 23000cp, 24000cp, 25000cp, etc.
The third object of the present invention is to provide a method for preparing the polyimide precursor glue solution, which comprises the steps of: mixing dianhydride monomer, diamine monomer and solvent to perform 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 (3) dissolving diamine monomer in a solvent, cooling, adding dianhydride monomer under nitrogen atmosphere, and stirring to obtain polyimide precursor glue solution.
Preferably, the cooling temperature is 8 to 12 ℃, for example 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 ℃, etc.
Preferably, the stirring time is 6 to 10 hours, for example 7 hours, 8 hours, 9 hours, etc.
The fourth object of the present invention is to provide a polyimide, especially a polyimide applied to a flexible copper clad laminate, wherein the polyimide is obtained by imidizing a polyimide precursor of one object or a polyimide precursor glue of two objects.
Preferably, the polyimide has a thermal expansion coefficient 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, etc.
Preferably, the polyimide has a glass transition temperature of 320 to 400 ℃, for example 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃, and the like.
The invention aims to provide a flexible copper-clad plate, in particular to a glue-free flexible copper-clad plate, which comprises a copper foil and an insulating layer, wherein the insulating layer contains polyimide with the purpose of four.
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, etc.
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, etc.
The invention aims at providing a preparation method of the flexible copper-clad plate, which comprises the following steps: coating the polyimide precursor glue solution for two purposes on the copper foil, and imidizing to obtain the flexible copper-clad plate.
Preferably, the imidization method includes baking.
Preferably, the baking includes a first baking and a second baking.
Preferably, the time of the first baking is 2 to 5min, for example, 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, etc.
Preferably, the temperature of the first baking is 150 to 180 ℃, for example 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 178 ℃, etc.
Preferably, the time of the second baking is 20 to 40min, for example, 22min, 24min, 26min, 28min, 30min, 32min, 34min, 36min, 38min, etc.
Preferably, the temperature of the second baking is 350 to 400 ℃, for example 360 ℃, 370 ℃, 380 ℃, 390 ℃, etc.
Preferably, the second baking is performed under the protection of nitrogen.
Preferably, the preparation method comprises the following steps:
coating the polyimide precursor glue solution for two purposes on a copper foil, baking for 2-5 min at the temperature of 150-180 ℃ for the first time, and then baking for 20-40 min at the temperature of 350-400 ℃ for the second time under the protection of nitrogen, so as to obtain the flexible copper-clad plate.
The invention aims at providing a printed circuit board which comprises the flexible copper clad laminate.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, BIA is firstly introduced into a polyimide precursor raw material formula, the polyimide synthesized by BIA has very low CTE, and because imidazole can form a complex with copper foil, good peel strength is maintained; meanwhile, a diamine monomer A containing a small side group is introduced into a raw material formula of the polyimide precursor, and the diamine monomer A is matched with BIA, so that the final polyimide can keep a very low CTE, and the precursor polyamic acid can keep a relatively large CTE, the shrinkage of a glue layer in the coating heating process is reduced, the problem that the coating processing process is easy to fold is solved, and the peeling strength of the flexible copper clad laminate is improved.
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 peeling strength of the copper-clad plate is 1.16-1.51N/mm.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
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) benzimidazol-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 slowly added under a nitrogen flow; stirring is continued for 8 hours to prepare polyimide resin precursor glue solution, and the viscosity is 20000cp. Wherein the mass ratio of BIA to m-TB is 3.7:1.
2) Coating the polyimide resin precursor glue solution on a 12 mu m rolled copper foil, baking for 4min at 160 ℃, then baking for 30min at 390 ℃ in an oven under the protection of nitrogen, and finally, imidizing the polyimide precursor to obtain the single-sided flexible copper-clad plate with the thickness of an insulating layer of 25 mu m.
Example 2
The difference from example 1 is that BIA is added in an amount of 8.77 g, m-TB in an amount of 3.19 g, and the mass ratio of BIA to m-TB is 2.7:1.
Example 3
The difference from example 1 is that BIA is added in an amount of 8.10 g, m-TB is added in an amount of 3.83 g, and the mass ratio of BIA to m-TB is 2.1:1.
Example 4
The difference from example 1 is that BIA is added in an amount of 7.42 g, m-TB in an amount of 4.47 g, and the mass ratio of BIA to m-TB is 1.7:1.
Example 5
The difference from example 1 is that BIA is added in an amount of 6.75 g, m-TB is added in an amount of 5.11 g, and the mass ratio of BIA to m-TB is 1.3:1.
Example 6
The difference from example 1 is that BIA is added in an amount of 6.07 g and m-TB in an amount of 5.79 g, and the mass ratio of BIA to m-TB is 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) benzimidazol-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) were dissolved in N-methylpyrrolidone (NMP) with stirring; the resulting solution was then cooled to 8 ℃ in a water bath and 12.98 grams of pyromellitic dianhydride (PMDA) was slowly added under a nitrogen flow; stirring was continued for 6 hours to prepare a polyimide resin precursor dope with a viscosity of 15000cp. Wherein the mass ratio of the 2- (diaminophenyl) 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 mu m rolled copper foil, baking for 5min at 150 ℃, and baking for 40min at 350 ℃ in an oven under the protection of nitrogen to finish imidization of the polyimide precursor, thus obtaining the single-sided flexible copper-clad plate with the thickness of an insulating layer of 3 mu m.
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) benzimidazol-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' -diphenylether dianhydride (ODPA) was slowly added under a nitrogen flow; stirring was continued for 10 hours to prepare a polyimide resin precursor dope having a viscosity of 25000cp. Wherein the mass ratio of the 2- (diaminophenyl) benzimidazole-5 amine to the 4,4 '-diamino-2, 2' -dimethyl-6, 6 '-trifluoromethyl-1, 1' -biphenyl diamine is 2.8:1.
2) Coating the polyimide resin precursor glue solution on a 12 mu m rolled copper foil, baking for 2min at 180 ℃, and baking for 20min at 400 ℃ in an oven under the protection of nitrogen to finish imidization of the polyimide precursor, thus obtaining the single-sided flexible copper-clad plate with the thickness of an insulating layer of 37 mu m.
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) 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 slowly added under a nitrogen flow; continuously stirring for 8 hours to prepare polyimide resin precursor glue solution, wherein the viscosity is controlled between 20000cp.
2) Coating the polyimide resin precursor glue solution on a 12 mu m rolled copper foil, baking for 4min at 160 ℃, then baking for 30min at 390 ℃ in an oven under the protection of nitrogen, and finally, imidizing the polyimide precursor to obtain the single-sided flexible copper-clad plate with the thickness of an insulating layer of 25 mu m.
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) 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 slowly added under a nitrogen flow; continuously stirring for 8 hours to prepare polyimide resin precursor glue solution, wherein the viscosity is controlled between 20000cp.
2) Coating the polyimide resin precursor glue solution on a 12 mu m rolled copper foil, baking for 4min at 160 ℃, then baking for 30min at 390 ℃ in an oven under the protection of nitrogen, and finally, imidizing the polyimide precursor to obtain the single-sided flexible copper-clad plate with the thickness of an insulating layer of 25 mu m.
Comparative example 3
The difference from example 2 is that BIA was not added and the amount of m-TB added was 11.96g.
Comparative example 4
The difference from example 2 is that BIA is added in an amount of 9.8 g, m-TB is added in an amount of 2.16 g, and the mass ratio of BIA to m-TB is 4.5:1.
Comparative example 5
The difference from example 2 is that BIA is added in an amount of 5.4 g, m-TB is added in an amount of 6.56 g, and the mass ratio of BIA to m-TB is 0.8:1.
Performance testing
The performance of the flexible copper clad laminates of the examples and comparative examples was tested and the test results were recorded in table 1.
The test method of the characteristics is as follows:
peel Strength (PS): the peeling strength of the metal layer at 90 degrees is tested according to the IPC-TM-650.2.4.9 method;
coefficient of Thermal Expansion (CTE): etching the flexible copper clad laminate copper foil to obtain a sample, heating the sample to 350 ℃ at a speed of 5 ℃/min in a Thermal Mechanical Analyzer (TMA) to obtain a thermal expansion coefficient between 100 ℃ and 250 ℃;
the single-sided flexible copper-clad plate after coating and baking is folded: the folding condition was visually checked and the height of warpage due to folding was measured with a ruler.
TABLE 1
Peel strength (N/mm) CTE(ppm/℃) Warp height (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 formed into a cylinder shape
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 shown in Table 1, the polyimide precursor provided by the invention can be used for preparing the glue-free flexible copper-clad plate with smaller polyimide CTE, and the obtained flexible copper-clad plate has good peeling strength, and can not generate a turnover phenomenon in the coating processing process, wherein the CTE of the polyimide is 3.2-12.6 ppm/DEG C, the warping height after coating and baking is 1.8-5.2 cm, and the peeling strength of the copper-clad plate is 1.16-1.51N/mm.
In the case of using BIA alone, the comparative example 1 is coated and folded into a cylinder, and the peel strength of the copper-clad plate is low; comparative example 3 m-TB alone, polyimide has too large CTE and low application value.
In comparative example 2, where BIA and m-TB were not used, CTE was large.
As is clear from comparative examples 1 to 6 and comparative examples 4 to 5, the coating warpage level was decreased with the increase in the amount of m-TB (diamine monomer A) and the decrease in the amount of BIA, but CTE was gradually increased, and three properties were balanced only when the ratio of the two was adjusted to (1 to 4): 1 (examples 1 to 6), and particularly when the ratio was adjusted to (1.5 to 3): 1 (examples 2 to 4), three properties of polyimide CTE, coating warpage level, and peel strength of the flexible copper clad laminate could be further balanced.
The present invention is described in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e., it does not mean that the present invention must be practiced depending on the above detailed methods. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (26)

1. Polyimide applied to flexible copper clad laminate is characterized in that the polyimide is obtained by imidizing polyimide precursor glue solution;
the preparation method of the polyimide precursor glue solution comprises the following steps: mixing dianhydride monomer, diamine monomer and solvent to perform polycondensation reaction to obtain polyimide precursor glue solution;
the diamine monomer comprises 2- (diaminophenyl) benzimidazole-5 amine and diamine monomer A;
Figure FDA0004167173080000011
the R is 1 ～R 8 Each independently selected from-H, -F, -CH 3 or-CF 3 Provided that R 1 ～R 4 At least one of them is selected from-CH 3 or-CF 3 And R is 5 ～R 8 At least one of them is selected from-CH 3 or-CF 3 ；
The mass ratio of the 2- (diaminophenyl) benzimidazole-5 amine to the diamine monomer A is (1-4): 1.
2. The polyimide according to claim 1, wherein the mass ratio of 2- (diaminophenyl) benzimidazol-5 amine to diamine monomer A is 1.5 to 3:1.
3. The polyimide according to claim 1, wherein the sum of the mass of the 2- (diaminophenyl) benzimidazol-5 amine and the mass of the diamine monomer a is 30 to 95% of the total mass of the diamine monomer.
4. The polyimide according to claim 1, 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.
5. The polyimide according to claim 1, characterized in that the diamine monomer further comprises 4,4' -diaminodiphenyl ether and/or p-phenylenediamine.
6. The polyimide according to claim 1, wherein the dianhydride monomer comprises any one or a combination of at least two of biphenyl dianhydride, pyromellitic dianhydride, or 4,4' -diphenyl ether dianhydride.
7. Polyimide according to claim 1, characterized in that the solvent comprises N-methylpyrrolidone and/or N, N' -dimethylacetamide.
8. The polyimide according to claim 1, wherein the polyimide precursor dope has a viscosity of 15000 to 25000cp.
9. The polyimide according to claim 1, wherein the preparation method of the polyimide precursor glue solution specifically comprises the following steps: and (3) dissolving diamine monomer in a solvent, cooling, adding dianhydride monomer under nitrogen atmosphere, and stirring to obtain polyimide precursor glue solution.
10. The polyimide according to claim 9, wherein the cooling temperature is 8 to 12 ℃.
11. The polyimide according to claim 9, wherein the stirring time is 6 to 10 hours.
12. The polyimide according to claim 1, wherein the polyimide has a thermal expansion coefficient of 2 to 10ppm/°c.
13. The polyimide according to claim 1, wherein the polyimide has a glass transition temperature of 320 to 400 ℃.
14. 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 as defined in any one of claims 1 to 13.
15. The flexible copper clad laminate of claim 14 wherein the insulating layer has a thickness of 3 to 37 μm.
16. The flexible copper clad laminate of claim 14 wherein the copper foil has a thickness of 9 to 70 μm.
17. A method of producing a flexible copper clad laminate according to any one of claims 14 to 16, characterized in that the method of producing comprises: coating polyimide precursor glue solution on the copper foil, and obtaining a flexible copper-clad plate after imidization;
the preparation method of the polyimide precursor glue solution comprises the following steps: mixing dianhydride monomer, diamine monomer and solvent to perform polycondensation reaction to obtain polyimide precursor glue solution;
the diamine monomer comprises 2- (diaminophenyl) benzimidazole-5 amine and diamine monomer A;
Figure FDA0004167173080000031
the R is 1 ～R 8 Each independently selected from-H, -F, -CH 3 or-CF 3 Provided that R 1 ～R 4 At least one of them is selected from-CH 3 or-CF 3 And R is 5 ～R 8 At least one of them is selected from-CH 3 or-CF 3 ；
The mass ratio of the 2- (diaminophenyl) benzimidazole-5 amine to the diamine monomer A is (1-4): 1.
18. The method of claim 17, wherein the imidizing process comprises baking.
19. The method of preparing according to claim 18, wherein the baking comprises a first baking and a second baking.
20. The method of claim 19, wherein the first baking is for a period of 2 to 5 minutes.
21. The method of claim 19, wherein the first baking is performed at a temperature of 150 to 180 ℃.
22. The method of claim 19, wherein the second baking is performed for 20 to 40 minutes.
23. The method of claim 19, wherein the second baking is performed at a temperature of 350 to 400 ℃.
24. The method of claim 19, wherein the second baking is performed under nitrogen.
25. The method of manufacturing according to claim 19, characterized in that the method of manufacturing comprises:
coating the polyimide precursor glue solution on a copper foil, baking for 2-5 min at 150-180 ℃ for the first time, and then baking for 20-40 min at 350-400 ℃ for the second time under the protection of nitrogen gas to obtain the flexible copper-clad plate.
26. A printed circuit board comprising the flexible copper clad laminate of any one of claims 14 to 16.
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