Method for synthesizing polyimide precursor polymer resin and method for manufacturing single-sided flexible copper-clad plates

Abstract

The invention relates to a method for synthesizing polyimide precursor polymer resin and a method for manufacturing single-sided flexible copper-clad plates, which are applied to the technical field of microelectronics. An adhesive-free single-sided flexible copper-clad plate is obtained by the steps of: dissolving a monomer aromatic diamine in a non-proton polar solvent, stirring for dissolution, adding a silane coupling agent, stirring, adding an aromatic dianhydride monomer for polymerization to generate a polyimide precursor polymer resin solution, reacting and standing for defoaming; andcoating resin on a copper foil, pre-baking in an oven, removing the solvent, and heating in a gradient way in the high-temperature non-oxidation over (importing with nitrogen) so as to carry out complete imidization. The single-sided flexible copper-clad plate has the advantages that the heat resistance is good, the dimensional stability is strong, a substrate is thin, the peel strength is not less than 1.1kgf / cm, the polyimide resin is smooth and level after total etching, the elongation percentage is not less than 35%, the tensile strength is not less than 250MPa, the heat resistant temperature Tg of a polyimide insulation layer is not less than 328DEG C, and meanwhile, the plate has lower heat expansion coefficient, dielectric constant and water absorption rate.

Description

technical field

[0001] The invention relates to the technical field of microelectronic materials, in particular to a method for synthesizing a polyimide prepolymer resin for an adhesive-free single-sided flexible copper-clad laminate and a method for manufacturing the single-sided flexible copper-clad laminate. Background technique

[0002] Flexible printed circuit board, referred to as soft board, has the advantages of softness, lightness, thinness and flexibility. With the rapid trend of electronic products becoming lighter, thinner, shorter and smaller, it has been widely used in notebook computers, digital cameras, Mobile phones, liquid crystal displays and other electronic fields.

[0003] Traditional soft board materials are mainly based on the three-layer structure of polyimide film / adhesive / copper foil, such as figure 1 As shown, the adhesive is mainly acrylic, and the soft board material with this structure has the following defects:

[0004] 1. Poor heat resistan...

Examples

Embodiment 1

[0079] Add 216 grams of DMAc to a three-neck vessel with nitrogen gas, then add 6.1 grams (0.03 moles) of ODA and 7.6 grams (0.07 moles) of PPDA, stir and dissolve completely at 50 ° C, and then add 0.5 grams of silane coupling reagent KBM-603 After stirring for 30 minutes, add 5.5 grams (0.025 moles) of PMDA at 0°C (ice-water bath), add 19.8 grams (0.07 moles) of BPDA after stirring for 1.5 hours, and continue stirring for 6 hours to obtain polyimide prepolymer resin , Standing defoaming, the measured resin solid content is 16.2%, and the viscosity is 14200CPS.

[0080] Coat the above-mentioned polyimide prepolymer resin on JE BHY-22BT type 1 / 2oz RA Copper, pre-bake it in an oven at 160°C / 5 minutes, remove the solvent, and then heat it at a high temperature under nitrogen protection In a non-oxidizing oven, the temperature is gradually increased at 80°C / 30 minutes, 120°C / 60 minutes, 160°C / 30 minutes, 200°C / 30 minutes, 250°C / 30 minutes, 300°C / 20 minutes, 330°C / 30 minutes , so...

Embodiment 2

[0082] In a three-necked container with nitrogen, add 327 grams of DMF, then add 12.1 grams (0.06 moles) of ODA and 16.4 grams (0.04 moles) of BAPP, stir and dissolve completely at room temperature, and then add 0.9 grams of silane coupling reagent KBM-403 After stirring for 30 minutes, add 9.7 grams (0.03 moles) of BTDA at 0°C (ice-water bath), add 20.6 grams (0.07 moles) of BPDA after stirring for 2 hours, and continue stirring for 7 hours to obtain a polyimide prepolymer resin , standing defoaming, the measured solid content of the resin is 15.8%, and the viscosity is 13700CPS.

[0083] Coat the above-mentioned polyimide prepolymer resin on JE JTCS type 1 / 2oz ED Copper, pre-bake it in an oven at 160°C / 5 minutes to remove the solvent, and then put it under the protection of nitrogen at high temperature without oxidation In the oven, the temperature is gradually increased at 80°C / 30 minutes, 120°C / 60 minutes, 160°C / 30 minutes, 200°C / 30 minutes, 250°C / 30 minutes, 300°C / 20 minu...

Embodiment 3

[0085] In a three-necked container with nitrogen gas, add 219 grams of NMP, then add 8.7 grams (0.08 moles) of PPDA and 5.8 grams (0.02 moles) of TPER, stir and dissolve completely at 50 ° C, and then add 0.8 grams of silane coupling reagent KBM- 603, after stirring for 30 minutes, add 25 grams (0.085 moles) of BPDA at 0°C (ice-water bath), add 6.2 grams (0.02 moles) of ODPA after stirring for 2 hours, and continue stirring for 8 hours to obtain a polyimide prepolymer Resin, standing defoaming, measured resin solid content is 17.3%, viscosity is 17500CPS.

[0086] Coat the above-mentioned polyimide prepolymer resin on "Fukuda 1 / 2oz ED Copper", pre-bake it in an oven at 170°C / 10 minutes to remove the solvent, and then place it in a high-temperature non-oxidizing oven under nitrogen protection to 80°C / 30 minutes, 120°C / 60 minutes, 160°C / 30 minutes, 200°C / 30 minutes, 250°C / 30 minutes, 300°C / 20 minutes, 350°C / 30 minutes to make imide After complete melting, an adhesive-free singl...

technical field

[0001] The invention relates to the technical field of microelectronic materials, in particular to a method for synthesizing a polyimide prepolymer resin for an adhesive-free single-sided flexible copper-clad laminate and a method for manufacturing the single-sided flexible copper-clad laminate. Background technique

[0002] Flexible printed circuit board, referred to as soft board, has the advantages of softness, lightness, thinness and flexibility. With the rapid trend of electronic products becoming lighter, thinner, shorter and smaller, it has been widely used in notebook computers, digital cameras, Mobile phones, liquid crystal displays and other electronic fields.

[0003] Traditional soft board materials are mainly based on the three-layer structure of polyimide film / adhesive / copper foil, such as figure 1 As shown, the adhesive is mainly acrylic, and the soft board material with this structure has the following defects:

[0004] 1. Poor heat resistan...

Examples

Embodiment 1

[0079] Add 216 grams of DMAc to a three-neck vessel with nitrogen gas, then add 6.1 grams (0.03 moles) of ODA and 7.6 grams (0.07 moles) of PPDA, stir and dissolve completely at 50 ° C, and then add 0.5 grams of silane coupling reagent KBM-603 After stirring for 30 minutes, add 5.5 grams (0.025 moles) of PMDA at 0°C (ice-water bath), add 19.8 grams (0.07 moles) of BPDA after stirring for 1.5 hours, and continue stirring for 6 hours to obtain polyimide prepolymer resin , Standing defoaming, the measured resin solid content is 16.2%, and the viscosity is 14200CPS.

[0080] Coat the above-mentioned polyimide prepolymer resin on JE BHY-22BT type 1 / 2oz RA Copper, pre-bake it in an oven at 160°C / 5 minutes, remove the solvent, and then heat it at a high temperature under nitrogen protection In a non-oxidizing oven, the temperature is gradually increased at 80°C / 30 minutes, 120°C / 60 minutes, 160°C / 30 minutes, 200°C / 30 minutes, 250°C / 30 minutes, 300°C / 20 minutes, 330°C / 30 minutes , so...

Embodiment 2

[0082] In a three-necked container with nitrogen, add 327 grams of DMF, then add 12.1 grams (0.06 moles) of ODA and 16.4 grams (0.04 moles) of BAPP, stir and dissolve completely at room temperature, and then add 0.9 grams of silane coupling reagent KBM-403 After stirring for 30 minutes, add 9.7 grams (0.03 moles) of BTDA at 0°C (ice-water bath), add 20.6 grams (0.07 moles) of BPDA after stirring for 2 hours, and continue stirring for 7 hours to obtain a polyimide prepolymer resin , standing defoaming, the measured solid content of the resin is 15.8%, and the viscosity is 13700CPS.

[0083] Coat the above-mentioned polyimide prepolymer resin on JE JTCS type 1 / 2oz ED Copper, pre-bake it in an oven at 160°C / 5 minutes to remove the solvent, and then put it under the protection of nitrogen at high temperature without oxidation In the oven, the temperature is gradually increased at 80°C / 30 minutes, 120°C / 60 minutes, 160°C / 30 minutes, 200°C / 30 minutes, 250°C / 30 minutes, 300°C / 20 minu...

Embodiment 3

[0085] In a three-necked container with nitrogen gas, add 219 grams of NMP, then add 8.7 grams (0.08 moles) of PPDA and 5.8 grams (0.02 moles) of TPER, stir and dissolve completely at 50 ° C, and then add 0.8 grams of silane coupling reagent KBM- 603, after stirring for 30 minutes, add 25 grams (0.085 moles) of BPDA at 0°C (ice-water bath), add 6.2 grams (0.02 moles) of ODPA after stirring for 2 hours, and continue stirring for 8 hours to obtain a polyimide prepolymer Resin, standing defoaming, measured resin solid content is 17.3%, viscosity is 17500CPS.

[0086] Coat the above-mentioned polyimide prepolymer resin on "Fukuda 1 / 2oz ED Copper", pre-bake it in an oven at 170°C / 10 minutes to remove the solvent, and then place it in a high-temperature non-oxidizing oven under nitrogen protection to 80°C / 30 minutes, 120°C / 60 minutes, 160°C / 30 minutes, 200°C / 30 minutes, 250°C / 30 minutes, 300°C / 20 minutes, 350°C / 30 minutes to make imide After complete melting, an adhesive-free singl...

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