Polyimide, method for preparing the same, and polyester electronic adhesive

Abstract

This invention discloses polyimide, its preparation method, and polyester electronic adhesive. This invention provides a polyimide whose polymerizing monomers include dianhydride monomers and diamine monomers, wherein the dianhydride monomer is selected from one or more of 4,4'-(4,4'-isopropyldiphenoxy)bis(phthalic anhydride), 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxybis(phthalic anhydride), and 2,3,3',4'-biphenyltetracarboxylic dianhydride; and the diamine monomer is selected from one or more of aminophenyl sulfone, 1,3-bis(4'-aminophenoxy)benzene, 2,2'-bis[4-(4-aminophenoxyphenyl)]propane, 4,4'-bis(3-aminophenoxy)diphenyl sulfone, 1,3-cyclohexanedimethylamine, 4,4'-diaminodiphenyl ether, dimericadiamine, and trimericadiamine. The polyimide of this invention can modify polyester or epoxy systems, significantly improving flame retardancy and adhesive peel strength. The coating process involves evaporation at relatively low temperatures, and the solvent in the system has a low boiling point, meeting the requirements of existing processes.

Description

Technical Field

[0001] This invention relates to polyimide, its preparation method, and polyester-containing electronic adhesive. Background Technology

[0002] Currently, the adhesives used in domestic flexible copper clad laminates (FCCLs) are mostly epoxy or polyester-based, which generally do not meet the required flame retardant properties. Inorganic powder solids (hydroxides) or phosphorus-based flame retardants need to be added, which leads to a decrease in adhesion or electrical properties. Using polyimide (PI) adhesives often requires sophisticated processing equipment, including high-temperature and high-pressure equipment. Summary of the Invention

[0003] To address the limitation of selectivity in existing polyester electronic adhesives, this invention provides a polyimide, its preparation method, and the polyester electronic adhesive. The polyimide of this invention can modify polyester or epoxy systems, significantly improving flame retardant properties and adhesive peel strength. The coating process involves evaporation at a relatively low temperature, and the solvent in the system has a low boiling point, meeting the requirements of existing processes.

[0004] This invention provides a polyimide whose polymerization monomers include dianhydride monomers and diamine monomers. The dianhydride monomers are selected from one or more of BPADA (4,4'-(4,4'-isopropyldiphenoxy)bis(phthalic anhydride)), BTDA (3,3',4,4'-benzophenone tetracarboxylic dianhydride), ODPA (4,4'-oxybisphthalic anhydride), and α-BPDA (2,3,3',4'-biphenyl tetracarboxylic dianhydride). The diamine monomers are selected from one or more of DDS (aminophenyl sulfone), TPE-R (1,3-bis(4'-aminophenoxy)benzene), BAPP (2,2'-bis[4-(4-aminophenoxyphenyl)]propane), BAPS-M (4,4'-bis(3-aminophenoxy)diphenyl sulfone), 1,3-BAC (1,3-cyclohexanedimethylamine), ODA (4,4'-diaminodiphenyl ether), dimericamine, and trimericamine.

[0005] In one embodiment, the dianhydride monomers are BPADA and α-BPDA, for example, the molar ratio of BPADA to α-BPDA is 1:1;

[0006] Alternatively, the dianhydride monomers may be ODPA and BPADA, for example, the molar ratio of ODPA and BPADA may be 1:1.

[0007] In one embodiment, the diamine monomer is dimericamine Priamine 1075.

[0008] In one embodiment, the molar ratio of the diamine monomer to the dianhydride monomer is (0.7-1.2):1, for example, 0.9:1.

[0009] In one embodiment, the dianhydride monomers are BPADA and α-BPDA, with a molar ratio of BPADA to α-BPDA of 1:1; the diamine monomer is diamine Priamine 1075; and the molar ratio of the diamine monomer to the dianhydride monomer is 0.9:1.

[0010] Alternatively, the dianhydride monomers are ODPA and BPADA, with a molar ratio of ODPA to BPADA of 1:1; the diamine monomer is diamine Priamine 1075; and the molar ratio of the diamine monomer to the dianhydride monomer is 0.9:1.

[0011] This invention provides a method for preparing polyimide, comprising the following steps: an imidization reaction of a dianhydride monomer and a diamine monomer at 60℃-150℃ to obtain the polyimide; wherein the dianhydride monomer is selected from BPADA (4,4'-(4,4'-isopropyldiphenoxy)bis(phthalic anhydride)), BTDA (3,3',4,4'-benzophenone tetracarboxylic dianhydride), ODPA (4,4'-oxybis(phthalic anhydride)), and α-BPDA (2,3,3',4'-diphenyl ether tetracarboxylic dianhydride). One or more of '-biphenyltetracarboxylic dianhydride), wherein the diamine monomer is selected from one or more of DDS (aminophenyl sulfone), TPE-R (1,3-bis(4'-aminophenoxy)benzene), BAPP (2,2'-bis[4-(4-aminophenoxyphenyl)]propane), BAPS-M (4,4'-bis(3-aminophenoxy)diphenyl sulfone), 1,3-BAC (1,3-cyclohexanedimethylamine), ODA (4,4'-diaminodiphenyl ether), dimericamine, and trimericamine.

[0012] In one embodiment, the dianhydride monomer and the diamine monomer participate in the reaction in solution form.

[0013] In one embodiment, the solvent of the solution is selected from one or more of ketone solvents, hydrocarbon solvents, and ester solvents. The ketone solvent is, for example, cyclobutanone. The hydrocarbon solvent is, for example, aromatic hydrocarbons and / or alkane solvents. The aromatic hydrocarbon solvent is, for example, toluene and / or xylene. The alkane solvent is, for example, methylcyclohexane. Another example is that the solvent of the solution is a mixed solvent of cyclohexanone and methylcyclohexane. Yet another example is that the mass ratio of cyclohexanone to methylcyclohexane is (6-10):1, or even 9:1.

[0014] In one embodiment, the mass ratio of the solvent to the dianhydride monomer in the solution is (8-12):1. For example, it could be 10:1.

[0015] In one embodiment, the mass ratio of the solvent to the diamine monomer in the solution is (8-12):1. For example, it could be 10:1.

[0016] In one embodiment, the diamine monomer is added to the dianhydride monomer for reaction; for example, the diamine monomer is added to the dianhydride monomer for reaction at 60°C.

[0017] In one embodiment, the dianhydride monomer is as described in any of the preceding embodiments.

[0018] In one embodiment, the diamine monomer is as described in any of the preceding embodiments.

[0019] This invention provides a polyimide prepared by the above-described method for preparing polyimide.

[0020] In one embodiment, the polyimide of the present invention is in the form of a soluble solution.

[0021] In one embodiment, the polyimide of the present invention can be soluble in one or more of butanone, cyclohexanone, toluene, xylene, DMF, methylcyclohexane, and ethyl acetate.

[0022] This invention provides the application of the polyimide described above as a modifier in the preparation of compositions for polyester electronic adhesives or polyester electronic adhesives.

[0023] In one embodiment, the addition of the polyimide of the present invention to the polyester electronic adhesive can improve the flame retardant properties of the system.

[0024] In one embodiment, the polyimide of the present invention, when added to the polyester electronic adhesive, can improve the peel strength of the system.

[0025] The present invention provides a composition for use in polyester electronic adhesives, comprising 90-95 parts by weight of polyester, 250-270 parts by weight of ketone solvent, 0.3-1 parts by weight of polyimide as described in any of the preceding embodiments, 2-5 parts by weight of epoxy resin, 5-10 parts by weight of halogen-free flame retardant and 3-6 parts by weight of isocyanate.

[0026] In one embodiment, the polyester is a copolyester, for example, selected from one or more of copolyesters Vylon 560, Vylon 600, and Vylon 290.

[0027] In one embodiment, the ketone solvent is a fatty ketone solvent, such as butanone.

[0028] In one embodiment, the epoxy resin is a glycidyl ether type epoxy resin, such as a difunctional epoxy resin or a trifunctional epoxy resin, or more specifically, a difunctional epoxy resin YN-1828 or a trifunctional epoxy resin 304.

[0029] In one embodiment, the halogen-free flame retardant is an inorganic flame retardant and / or an organic flame retardant; the inorganic flame retardant is, for example, a hydroxide, or more specifically, aluminum hydroxide, and the organic flame retardant is, for example, HPCTP.

[0030] In one embodiment, the isocyanate is an aromatic isocyanate, such as isocyanate PDMI (polymethylene polyphenylene isocyanate), or isocyanate PM200 (Wanhua).

[0031] In one particular scheme, it contains 92 or 93 parts by mass of polyester.

[0032] In one particular formulation, 264 parts by mass of a ketone solvent are contained.

[0033] In one embodiment, it comprises 0.5 parts by mass of polyimide as described in any of the preceding embodiments.

[0034] In one particular formulation, it contains 2 or 3 parts by weight of epoxy resin.

[0035] One particular formulation contains 10 parts by weight of an inorganic flame retardant.

[0036] One particular formulation contains 5 parts by weight of an organic flame retardant.

[0037] In one particular formulation, it contains 4 parts by mass of isocyanate.

[0038] A given scheme may include or be any of the following:

[0039] Option 1: 92 parts by weight of copolyester, 264 parts by weight of ketone solvent, 0.5 parts by weight of polyimide as described in any of the previous options, 3 parts by weight of epoxy resin, 10 parts by weight of aluminum hydroxide, 5 parts by weight of HPCTP and 4 parts by weight of isocyanate;

[0040] Option 2: 93 parts by weight of copolyester, 264 parts by weight of ketone solvent, 0.5 parts by weight of polyimide as described in any of the previous options, 2 parts by weight of epoxy resin, 10 parts by weight of aluminum hydroxide, 5 parts by weight of HPCTP and 4 parts by weight of isocyanate.

[0041] A given scheme may include or be any of the following:

[0042] Option 1: 92 parts by weight of copolyester Vylon 560, 264 parts by weight of ketone solvent, 0.5 parts by weight of polyimide as described in any of the previous options, 3 parts by weight of difunctional epoxy resin YN-1828, 10 parts by weight of aluminum hydroxide, 5 parts by weight of HPCTP and 4 parts by weight of isocyanate PDMI;

[0043] Option 2: 92 parts by weight of copolyester Vylon 600, 264 parts by weight of ketone solvent, 0.5 parts by weight of polyimide as described in any of the previous options, 3 parts by weight of difunctional epoxy resin YN-1828, 10 parts by weight of aluminum hydroxide, 5 parts by weight of HPCTP and 4 parts by weight of isocyanate PDMI;

[0044] Option 3: 92 parts by weight of copolyester Vylon 290, 264 parts by weight of ketone solvent, 0.5 parts by weight of polyimide as described in any of the previous options, 3 parts by weight of difunctional epoxy resin YN-1828, 10 parts by weight of aluminum hydroxide, 5 parts by weight of HPCTP and 4 parts by weight of isocyanate PDMI;

[0045] Option 4: 93 parts by weight of copolyester Vylon 560, 264 parts by weight of ketone solvent, 0.5 parts by weight of polyimide as described in any of the previous options, 2 parts by weight of trifunctional epoxy resin 304, 10 parts by weight of aluminum hydroxide, 5 parts by weight of HPCTP and 4 parts by weight of isocyanate PDMI;

[0046] Option 5: 93 parts by weight of copolyester Vylon 600, 264 parts by weight of ketone solvent, 0.5 parts by weight of polyimide as described in any of the previous options, 2 parts by weight of trifunctional epoxy resin 304, 10 parts by weight of aluminum hydroxide, 5 parts by weight of HPCTP and 4 parts by weight of isocyanate PDMI;

[0047] Option 6: 93 parts by weight of copolyester Vylon 290, 264 parts by weight of ketone solvent, 0.5 parts by weight of polyimide as described in any of the previous options, 2 parts by weight of trifunctional epoxy resin 304, 10 parts by weight of aluminum hydroxide, 5 parts by weight of HPCTP and 4 parts by weight of isocyanate PDMI.

[0048] This invention provides a method for preparing a polyester electronic adhesive, the raw materials of which include: a polyester electronic adhesive composition as described in any of the preceding embodiments.

[0049] In one embodiment, the polyester is dissolved in the ketone solvent and mixed with the polyimide, epoxy resin, and halogen-free flame retardant.

[0050] In one embodiment, the polyester is dissolved in the ketone solvent, mixed with the polyimide, epoxy resin and halogen-free flame retardant, ground, then mixed with the isocyanate, coated and dried.

[0051] The present invention provides a polyester electronic adhesive, which is prepared from a polyester electronic adhesive composition as described in any of the preceding embodiments.

[0052] This invention provides a polyester electronic adhesive, which is prepared by the method for preparing polyester electronic adhesive as described in any of the preceding embodiments.

[0053] In one embodiment, the polyester electronic adhesive of the present invention has a flame retardancy rating of V0, and the test method refers to UL 94.

[0054] In one embodiment, the peel strength of the polyester electronic adhesive of the present invention is 2.5-3.0, for example 2.6, 2.7, 2.8, 2.9 or 3.0, and the test method refers to GB / T 2791.

[0055] In one embodiment, the polyester electronic adhesive of the present invention can be initially dried in an oven at 80~160°C, and the pressing temperature with copper foil can be below 200°C.

[0056] The present invention provides a flexible copper-clad laminate comprising a polyester electronic adhesive as described in any of the preceding embodiments.

[0057] Without violating common sense in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0058] The reagents and raw materials used in this invention are all commercially available.

[0059] The significant advantages of this invention are: the polyimide of this invention can modify polyester or epoxy systems, greatly improving flame retardant properties and adhesive peel strength. The coating process involves evaporation at a relatively low temperature, and the solvent in the system has a low boiling point, meeting the requirements of existing processes. Detailed Implementation

[0060] The present invention is further illustrated below by way of embodiments, but the invention is not limited to the scope of the embodiments described herein. Experimental methods in the following embodiments that do not specify specific conditions were performed according to conventional methods and conditions, or as selected according to the product instructions.

[0061] The abbreviations of compounds and their structural formulas in this invention are shown in the table below.

[0062]

[0063] Preparation Example 1: Synthesis process of soluble TPI-1 solution:

[0064] First, 29.42 g of α-BPDA monomer and 52.05 g of BPADA monomer were added to a reaction vessel. Then, 767.52 g of a mixture of cyclohexanone and methylcyclohexane (mass ratio of cyclohexanone to methylcyclohexane 9:1) was added to the reaction vessel. The mixture was stirred to form a solution or suspension, and the temperature was raised to 60°C. 108.14 g of dimeric amine Priamine 1075 was dissolved in a mixture of 973.30 g of cyclohexanone and methylcyclohexane (mass ratio of cyclohexanone to methylcyclohexane 9:1), and then slowly added to the reaction vessel containing the dianhydride suspension. The temperature was further increased from 60°C to 150°C, and the reaction was carried out for 20 hours until the imidization reaction was complete, yielding a soluble TPI-1 solution with a polyimide concentration of 10%. This solution was then set aside for later use.

[0065] Preparation Example 2: Synthesis process of soluble TPI-2 solution:

[0066] First, 31.02 g of ODPA monomer and 52.05 g of BPADA monomer were added to a reactor. Then, 767.52 g of a mixture of cyclohexanone and methylcyclohexane (mass ratio of cyclohexanone to methylcyclohexane 9:1) was added to the reactor. The mixture was stirred to form a solution or suspension, and the temperature was raised to 60°C. 108.14 g of dimeric amine Priamine 1075 was dissolved in a mixture of 973.30 g of cyclohexanone and methylcyclohexane (mass ratio of cyclohexanone to methylcyclohexane 9:1). This solution was then slowly added to the reactor containing the dianhydride suspension. The temperature was raised from 60°C to 150°C and the reaction was allowed to proceed for 20 hours until the imidization reaction was complete, yielding a soluble TPI-2 solution with a polyimide concentration of 10%. This solution was then set aside for later use.

[0067] Example 1

[0068] Take 92g of copolyester Vylon 560 and dissolve it in 264g of butanone. After the Vylon 560 is completely dissolved, add 3g of YN-1828, 10g of aluminum hydroxide, 5g of HPCTP, and 5g of homemade TPI-1 solution. Stir thoroughly to disperse, and grind twice with a grinder. Before use, add 4g of isocyanate PDMI, stir to mix evenly, and use within 48 hours. Coat the PI film using a coating machine, and then dry it in a segmented drying tunnel. The five drying temperatures are 90℃, 130℃, 170℃, 165℃, and 160℃, and the drying time in the tunnel is 4~8min, finally obtaining an 8μm thick adhesive layer. Press the coated PI film with copper foil in a vacuum hot press. The pressing conditions are: 20MPa, 180℃, 1min. The pressed samples were then aged in an oven with a stepped heating program: 60℃ for 2 hours, 80℃ for 4 hours, 100℃ for 2 hours, 120℃ for 1 hour, 160℃ for 1 hour, and then cooled for 1 hour to obtain fully aged samples for subsequent testing.

[0069] Example 2

[0070] Dissolve 92g of copolyester Vylon 600 in 264g of butanone. After Vylon 560 is completely dissolved, add 3g of YN-1828, 10g of aluminum hydroxide, 5g of HPCTP, and 5g of homemade TPI-1 solution. Stir thoroughly to disperse, and grind twice using a grinder. Before use, add 4g of isocyanate PDMI, stir to mix evenly, and use within 49 hours. Coat the PI film using a coating machine, and then dry it in a segmented drying tunnel. The five drying temperatures are 90℃, 130℃, 170℃, 165℃, and 160℃, and the drying time in the tunnel is 4~8min, finally obtaining an 8μm thick adhesive layer. Press the coated PI film with copper foil in a vacuum hot press under the following conditions: 20MPa, 180℃, 1min. The pressed samples were then aged in an oven with a stepped heating program: 60℃ for 2 hours, 80℃ for 4 hours, 100℃ for 2 hours, 120℃ for 1 hour, 160℃ for 1 hour, and then cooled for 1 hour to obtain fully aged samples for subsequent testing.

[0071] Example 3

[0072] Dissolve 92g of copolyester Vylon 290 in 264g of butanone. After Vylon 560 is completely dissolved, add 3g of YN-1828, 10g of aluminum hydroxide, 5g of HPCTP, and 5g of homemade TPI-1 solution. Stir thoroughly to disperse, and grind twice using a grinder. Before use, add 4g of isocyanate PDMI, stir to mix evenly, and use within 50 hours. Coat the PI film using a coating machine, and then dry it in a segmented drying tunnel. The five drying temperatures are 90℃, 130℃, 170℃, 165℃, and 160℃, and the drying time in the tunnel is 4~8min, finally obtaining an 8μm thick adhesive layer. Press the coated PI film with copper foil in a vacuum hot press under the following conditions: 20MPa, 180℃, 1min. The pressed samples were then aged in an oven with a stepped heating program: 60℃ for 2 hours, 80℃ for 4 hours, 100℃ for 2 hours, 120℃ for 1 hour, 160℃ for 1 hour, and then cooled for 1 hour to obtain fully aged samples for subsequent testing.

[0073] Example 4

[0074] Dissolve 93g of copolyester Vylon 560 in 264g of butanone. After the Vylon 560 is completely dissolved, add 2g of epoxy resin 304, 10g of aluminum hydroxide, 5g of HPCTP, and 5g of homemade TPI-2 solution. Stir thoroughly to disperse, and grind twice using a grinder. Before use, add 4g of isocyanate PDMI, stir to mix evenly, and use within 48 hours. Coat the PI film using a coating machine, and then dry it in a segmented drying tunnel. The five drying temperatures are 90℃, 130℃, 170℃, 165℃, and 160℃, and the drying time in the tunnel is 4~8min, finally obtaining an 8μm thick adhesive layer. Press the coated PI film with copper foil in a vacuum hot press under the following conditions: 20MPa, 180℃, 1min. The pressed samples were then aged in an oven with a stepped heating program: 60℃ for 2 hours, 80℃ for 4 hours, 100℃ for 2 hours, 120℃ for 1 hour, 160℃ for 1 hour, and then cooled for 1 hour to obtain fully aged samples for subsequent testing.

[0075] Example 5

[0076] Dissolve 93g of copolyester Vylon 600 in 264g of butanone. After Vylon 560 is completely dissolved, add 2g of epoxy resin 304, 10g of aluminum hydroxide, 5g of HPCTP, and 5g of homemade TPI-2 solution. Stir thoroughly to disperse, and grind twice using a grinder. Before use, add 4g of isocyanate PDMI, stir to mix evenly, and use within 48 hours. Coat the PI film using a coating machine, and then dry it in a segmented drying tunnel. The five drying temperatures are 90℃, 130℃, 170℃, 165℃, and 160℃, and the drying time in the tunnel is 4~8min, finally obtaining an 8μm thick adhesive layer. Press the coated PI film with copper foil in a vacuum hot press under the following conditions: 20MPa, 180℃, 1min. The pressed samples were then aged in an oven with a stepped heating program: 60℃ for 2 hours, 80℃ for 4 hours, 100℃ for 2 hours, 120℃ for 1 hour, 160℃ for 1 hour, and then cooled for 1 hour to obtain fully aged samples for subsequent testing.

[0077] Example 6

[0078] Dissolve 93g of copolyester Vylon 290 in 264g of butanone. After Vylon 560 is completely dissolved, add 2g of epoxy resin 304, 10g of aluminum hydroxide, 5g of HPCTP, and 5g of homemade TPI-2 solution. Stir thoroughly to disperse, and grind twice using a grinder. Before use, add 4g of isocyanate PDMI, stir to mix evenly, and use within 48 hours. Coat the PI film using a coating machine, and then dry it in a segmented drying tunnel. The five drying temperatures are 90℃, 130℃, 170℃, 165℃, and 160℃, and the drying time in the tunnel is 4~8min, finally obtaining an 8μm thick adhesive layer. Press the coated PI film with copper foil in a vacuum hot press under the following conditions: 20MPa, 180℃, 1min. The pressed samples were then aged in an oven with a stepped heating program: 60℃ for 2 hours, 80℃ for 4 hours, 100℃ for 2 hours, 120℃ for 1 hour, 160℃ for 1 hour, and then cooled for 1 hour to obtain fully aged samples for subsequent testing.

[0079] Comparative Example 1

[0080] Dissolve 97g of copolyester Vylon 560 in 280g of butanone. After the Vylon 560 is completely dissolved, add 3g of YN-1828, 15g of aluminum hydroxide, and 7g of HPCTP. Stir thoroughly to disperse the mixture and grind twice using a grinder. Before use, add 4g of isocyanate PDMI, stir to mix evenly, and use within 48 hours. Coat the PI film using a coating machine, and then dry it in a segmented drying tunnel. The five drying temperatures are 90℃, 130℃, 170℃, 165℃, and 160℃, and the drying time in the tunnel is 4~8min, finally obtaining an 8μm thick adhesive layer. Press the coated PI film with copper foil in a vacuum hot press under the following conditions: 20MPa, 180℃, 1min. The pressed samples were then aged in an oven with a stepped heating program: 60℃ for 2 hours, 80℃ for 4 hours, 100℃ for 2 hours, 120℃ for 1 hour, 160℃ for 1 hour, and then cooled for 1 hour to obtain fully aged samples for subsequent testing.

[0081] Comparative Example 2

[0082] Dissolve 97g of copolyester Vylon 600 in 280g of butanone. After Vylon 560 is completely dissolved, add 3g of YN-1828, 15g of aluminum hydroxide, and 7g of HPCTP. Stir thoroughly to disperse, and grind twice using a grinder. Before use, add 4g of isocyanate PDMI, stir to mix evenly, and use within 49 hours. Coat the PI film using a coating machine, and then dry it in a segmented drying tunnel. The five drying temperatures are 90℃, 130℃, 170℃, 165℃, and 160℃, and the drying time in the tunnel is 4~8min, finally obtaining an 8μm thick adhesive layer. Press the coated PI film with copper foil in a vacuum hot press under the following conditions: 20MPa, 180℃, 1min. The pressed samples were then aged in an oven with a stepped heating program: 60℃ for 2 hours, 80℃ for 4 hours, 100℃ for 2 hours, 120℃ for 1 hour, 160℃ for 1 hour, and then cooled for 1 hour to obtain fully aged samples for subsequent testing.

[0083] Comparative Example 3

[0084] Dissolve 97g of copolyester Vylon 290 in 280g of butanone. After Vylon 560 is completely dissolved, add 3g of YN-1828, 15g of aluminum hydroxide, and 7g of HPCTP. Stir thoroughly to disperse, and grind twice using a grinder. Before use, add 4g of isocyanate PDMI, stir to mix evenly, and use within 50 hours. Coat the PI film using a coating machine, and then dry it in a segmented drying tunnel. The five drying temperatures are 90℃, 130℃, 170℃, 165℃, and 160℃, and the drying time in the tunnel is 4~8min, finally obtaining an 8μm thick adhesive layer. Press the coated PI film with copper foil in a vacuum hot press under the following conditions: 20MPa, 180℃, 1min. The pressed samples were then aged in an oven with a stepped heating program: 60℃ for 2 hours, 80℃ for 4 hours, 100℃ for 2 hours, 120℃ for 1 hour, 160℃ for 1 hour, and then cooled for 1 hour to obtain fully aged samples for subsequent testing.

[0085] Comparative Example 4

[0086] Dissolve 98g of copolyester Vylon 560 in 280g of butanone. After the Vylon 560 is completely dissolved, add 2g of epoxy resin 304, 15g of aluminum hydroxide, and 7g of HPCTP. Stir thoroughly to disperse the mixture and grind twice using a grinder. Before use, add 4g of isocyanate PDMI, stir to mix evenly, and use within 48 hours. Coat the PI film using a coating machine, and then dry it in a segmented drying tunnel. The five drying temperatures are 90℃, 130℃, 170℃, 165℃, and 160℃, and the drying time in the tunnel is 4~8min, finally obtaining an 8μm thick adhesive layer. Press the coated PI film with copper foil in a vacuum hot press under the following conditions: 20MPa, 180℃, 1min. The pressed samples were then aged in an oven with a stepped heating program: 60℃ for 2 hours, 80℃ for 4 hours, 100℃ for 2 hours, 120℃ for 1 hour, 160℃ for 1 hour, and then cooled for 1 hour to obtain fully aged samples for subsequent testing.

[0087] Comparative Example 5

[0088] Dissolve 98g of copolyester Vylon 600 in 280g of butanone. After Vylon 560 is completely dissolved, add 2g of epoxy resin 304, 15g of aluminum hydroxide, and 7g of HPCTP. Stir thoroughly to disperse, and grind twice using a grinder. Before use, add 4g of isocyanate PDMI, stir to mix evenly, and use within 49 hours. Coat the PI film using a coating machine, and then dry it in a segmented drying tunnel. The five drying temperatures are 90℃, 130℃, 170℃, 165℃, and 160℃, and the drying time in the tunnel is 4~8min, finally obtaining an 8μm thick adhesive layer. Press the coated PI film with copper foil in a vacuum hot press under the following conditions: 20MPa, 180℃, 1min. The pressed samples were then aged in an oven with a stepped heating program: 60℃ for 2 hours, 80℃ for 4 hours, 100℃ for 2 hours, 120℃ for 1 hour, 160℃ for 1 hour, and then cooled for 1 hour to obtain fully aged samples for subsequent testing.

[0089] Comparative Example 6

[0090] Dissolve 98g of copolyester Vylon 290 in 280g of butanone. After Vylon 560 is completely dissolved, add 2g of epoxy resin 304, 15g of aluminum hydroxide, and 7g of HPCTP. Stir thoroughly to disperse, and grind twice using a grinder. Before use, add 4g of isocyanate PDMI, stir to mix evenly, and use within 50 hours. Coat the PI film using a coating machine, and then dry it in a segmented drying tunnel. The five drying temperatures are 90℃, 130℃, 170℃, 165℃, and 160℃, and the drying time in the tunnel is 4~8min, finally obtaining an 8μm thick adhesive layer. Press the coated PI film with copper foil in a vacuum hot press under the following conditions: 20MPa, 180℃, 1min. The pressed samples were then aged in an oven with a stepped heating program: 60℃ for 2 hours, 80℃ for 4 hours, 100℃ for 2 hours, 120℃ for 1 hour, 160℃ for 1 hour, and then cooled for 1 hour to obtain fully aged samples for subsequent testing.

[0091] The above embodiments and effect examples are summarized in the following table:

[0092]

[0093]

[0094] Example of effect test:

[0095] Drying temperature: Set the tunnel oven to five temperature sections of 90℃, 130℃, 170℃, 165℃, and 160℃. Set the speed of the conveyor chain so that the PI sample coated with electronic adhesive passes through the tunnel for 6 minutes. After exiting the tunnel oven, the solvent has basically evaporated.

[0096] Tg point: Refer to GB / T19466.2, specifically: Use a differential scanning calorimeter (DSC) instrument, set the scanning temperature range to -30℃~150℃, the heating rate to 5℃ / min, obtain the scanning curve, and find the corresponding Tg point on the curve.

[0097] Pressing temperature: Simply set the temperature of the pressing roller.

[0098] Peel strength: Refer to GB / T 2791, specifically:

[0099] Five 200mm x 25mm strips were cut from the prepared FCCL sample, with each strip having a glue-coated length greater than 150mm. These strips were then tested on a testing instrument with the clamp moving at 100mm / min and a test length greater than 125mm. The average peel force was calculated from the curve to obtain the peel force value for each strip. The average value was then calculated for all five test samples.

[0100] Flame retardancy rating: Refer to UL 94, specifically:

[0101] 1. Sample Preparation: Provide a compliant plastic sample, which must be cut to the specified dimensions and shape. Generally, the dimensions are: length 125mm * width 13mm * thickness 1.5mm.

[0102] 2. Flame Exposure: Place the sample vertically on the test rack and perform two 10-second burning tests on the lower end of the sample using a standard flame source.

[0103] 3. Observation and Recording: Record the time from the start of combustion to the extinguishing of the sample under the action of flame, observe and record whether there are drips during the combustion process and whether the sample continues to burn.

[0104] 4. Evaluation and Judgment: The flame retardant performance of the sample is evaluated based on the recorded parameters and the requirements of the UL94V-0 standard. If the sample meets all conditions, it is determined to meet the UL94V-0 flame retardant rating requirements.

[0105] Solder pot test: Set the temperature of the solder pot to 288℃, cut a sample about 2cm*2cm in size, immerse it in the molten solder for 20s, take out the sample and observe that the surface is flat without bumps and there is no delamination. If the surface is flat and there is no delamination, it is qualified and will not explode.

[0106]

Claims

1. A composition for use with polyester electronic adhesive, characterized in that, It contains 90-95 parts by weight of polyester, 250-270 parts by weight of ketone solvent, 0.3-1 parts by weight of polyimide, 2-5 parts by weight of epoxy resin, halogen-free flame retardant and 3-6 parts by weight of isocyanate; The halogen-free flame retardant is 5-10 parts by weight; or, the halogen-free flame retardant is 10 parts by weight of inorganic flame retardant and 5 parts by weight of organic flame retardant. The polymer monomers of the polyimide include dianhydride monomers and diamine monomers, wherein the dianhydride monomers are BPADA and α-BPDA; or, the dianhydride monomers are ODPA and BPADA, and the diamine monomer is dimericamine Priamine 1075.

2. The polyester electronic adhesive composition as described in claim 1, characterized in that, It meets one or more of the following conditions: (1) The polyester is a copolyester; (2) The ketone solvent is selected from fatty ketone solvents; (3) The epoxy resin is selected from glycidyl ether type epoxy resin; (4) The halogen-free flame retardant is an inorganic flame retardant and / or an organic flame retardant; (5) The isocyanate is an aromatic isocyanate; (6) The molar ratio of the diamine monomer to the dianhydride monomer is (0.7-1.2):1; (7) The polyimide is prepared by the following steps: under conditions of 60℃-150℃, the dianhydride monomer and the diamine monomer undergo an imidization reaction to obtain the polyimide; Its preparation method can satisfy one or more of the following conditions: 1) The dianhydride monomer and diamine monomer participate in the reaction in solution form: 2) The diamine monomer is added to the dianhydride monomer for reaction.

3. The polyester electronic adhesive composition as described in claim 1, characterized in that, It meets one or more of the following conditions: (1) The polyester is selected from one or more of copolyester Vylon 560, copolyester Vylon 600, and copolyester Vylon 290; (2) The ketone solvent is butanone; (3) The epoxy resin is a difunctional epoxy resin or a trifunctional epoxy resin; (4) The inorganic flame retardant is a hydroxide; (5) The organic flame retardant is HPCTP; (6) The isocyanate is PDMI isocyanate.

4. The polyester electronic adhesive composition as described in claim 1, characterized in that, It meets one or two of the following conditions: (1) The epoxy resin is a difunctional epoxy resin YN-1828 or a trifunctional epoxy resin 304. (2) The inorganic flame retardant is aluminum hydroxide.

5. The polyester electronic adhesive composition as described in claim 1, characterized in that, It meets one or more of the following conditions: (1) It contains 92 or 93 parts by weight of polyester; (2) It contains 264 parts by mass of ketone solvent; (3) It contains 0.5 parts by weight of polyimide; (4) It contains 2 or 3 parts by weight of epoxy resin; (5) It contains 10 parts by weight of inorganic flame retardant; (6) It contains 5 parts by weight of organic flame retardant; (7) It contains 4 parts by mass of isocyanate.

6. The polyester electronic adhesive composition as described in claim 1, characterized in that, It may include or be any of the following schemes: Option 1: 92 parts by weight of copolyester, 264 parts by weight of ketone solvent, 0.5 parts by weight of polyimide, 3 parts by weight of epoxy resin, 10 parts by weight of aluminum hydroxide, 5 parts by weight of HPCTP and 4 parts by weight of isocyanate; Option 2: 93 parts by weight of copolyester, 264 parts by weight of ketone solvent, 0.5 parts by weight of polyimide, 2 parts by weight of epoxy resin, 10 parts by weight of aluminum hydroxide, 5 parts by weight of HPCTP and 4 parts by weight of isocyanate.

7. The polyester electronic adhesive composition as described in claim 1, characterized in that, It may include or be any of the following schemes: Option 1: 92 parts by weight of copolyester Vylon 560, 264 parts by weight of ketone solvent, 0.5 parts by weight of polyimide, 3 parts by weight of difunctional epoxy resin YN-1828, 10 parts by weight of aluminum hydroxide, 5 parts by weight of HPCTP and 4 parts by weight of isocyanate PDMI; Option 2: 92 parts by weight of copolyester Vylon 600, 264 parts by weight of ketone solvent, 0.5 parts by weight of polyimide, 3 parts by weight of difunctional epoxy resin YN-1828, 10 parts by weight of aluminum hydroxide, 5 parts by weight of HPCTP and 4 parts by weight of isocyanate PDMI; Option 3: 92 parts by weight of copolyester Vylon 290, 264 parts by weight of ketone solvent, 0.5 parts by weight of polyimide, 3 parts by weight of difunctional epoxy resin YN-1828, 10 parts by weight of aluminum hydroxide, 5 parts by weight of HPCTP and 4 parts by weight of isocyanate PDMI; Option 4: 93 parts by weight of copolyester Vylon 560, 264 parts by weight of ketone solvent, 0.5 parts by weight of polyimide, 2 parts by weight of trifunctional epoxy resin 304, 10 parts by weight of aluminum hydroxide, 5 parts by weight of HPCTP and 4 parts by weight of isocyanate PDMI; Option 5: 93 parts by weight of copolyester Vylon 600, 264 parts by weight of ketone solvent, 0.5 parts by weight of polyimide, 2 parts by weight of trifunctional epoxy resin 304, 10 parts by weight of aluminum hydroxide, 5 parts by weight of HPCTP and 4 parts by weight of isocyanate PDMI; Option 6: 93 parts by weight of copolyester Vylon 290, 264 parts by weight of ketone solvent, 0.5 parts by weight of polyimide, 2 parts by weight of trifunctional epoxy resin 304, 10 parts by weight of aluminum hydroxide, 5 parts by weight of HPCTP and 4 parts by weight of isocyanate PDMI.

8. The polyester electronic adhesive composition as described in claim 2, characterized in that, It meets one or more of the following conditions: (1) The polyimide described herein satisfies one or two of the following conditions: 1) The molar ratio of BPADA to α-BPDA is 1:1; or, the molar ratio of ODPA to BPADA is 1:1; 2) The molar ratio of the diamine monomer to the dianhydride monomer is 0.9:1; (2) The polyimide is prepared by a method that satisfies one or more of the following conditions: 1) The diamine monomer is added to the dianhydride monomer at 60°C for reaction; 2) The solvent of the solution is selected from one or more of ketone solvents, hydrocarbon solvents, and ester solvents; 3) In the solution of the dianhydride monomer, the mass ratio of the solvent to the dianhydride monomer is (8-12):1; 4) In the solution of the diamine monomer, the mass ratio of the solvent to the diamine monomer is (8-12):

1.

9. The polyester electronic adhesive composition as described in claim 8, characterized in that, It meets one or more of the following conditions: (1) The dianhydride monomers are BPADA and α-BPDA, and the molar ratio of BPADA and α-BPDA is 1:1; the diamine monomer is diamine Priamine 1075; the molar ratio of the diamine monomer to the dianhydride monomer is 0.9:1; Alternatively, the dianhydride monomers are ODPA and BPADA, with a molar ratio of ODPA to BPADA of 1:1; the diamine monomer is diamine Priamine 1075; and the molar ratio of the diamine monomer to the dianhydride monomer is 0.9:

1. (2) The polyimide is prepared by a method that satisfies one or more of the following conditions: 1) The ketone solvent is cyclobutanone; 2) The hydrocarbon solvent is an aromatic hydrocarbon and / or alkane solvent; 3) The solvent of the solution is a mixture of cyclohexanone and methylcyclohexane; 4) In the solution of the dianhydride monomer, the mass ratio of the solvent to the dianhydride monomer is 10:1; 5) In the solution of the diamine monomer, the mass ratio of the solvent to the diamine monomer is 10:

1.

10. The polyester electronic adhesive composition as described in claim 9, characterized in that, The polyimide is prepared by a method that satisfies one or more of the following conditions: (1) The aromatic hydrocarbon solvent is toluene and / or xylene; (2) The alkane solvent is methylcyclohexane; (3) The mass ratio of cyclohexanone to methylcyclohexane is (6-10):

1.

11. The polyester electronic adhesive composition as described in claim 10, characterized in that, The polyimide is prepared in a manner that satisfies the following conditions: the mass ratio of cyclohexanone to methylcyclohexane is 9:

1.

12. A method for preparing a polyester electronic adhesive, characterized in that, Its raw materials include the polyester electronic adhesive composition as described in any one of claims 1-11.

13. The preparation method according to claim 12, characterized in that, It meets one or two of the following conditions: (1) The polyester is dissolved in the ketone solvent and mixed with the polyimide, epoxy resin and halogen-free flame retardant; (2) The polyester is dissolved in the ketone solvent, mixed with the polyimide, epoxy resin and halogen-free flame retardant, ground, mixed with the isocyanate, coated and dried.

14. A polyester electronic adhesive, which is prepared from the polyester electronic adhesive composition according to any one of claims 1-11, or prepared by the preparation method according to claim 12 or 13.

15. The polyester electronic adhesive as described in claim 14, characterized in that, It meets the following conditions: (1) The flame retardant rating of the polyester electronic adhesive is V0; (2) The peel force of the polyester electronic adhesive is 2.5-3.0 N / mm; (3) The polyester electronic adhesive can be initially dried in an oven at 80~160℃, and the pressing temperature with the copper foil is below 200℃.

16. The polyester electronic adhesive as described in claim 14, characterized in that, The peel strength of the polyester electronic adhesive is 2.6, 2.7, 2.8, 2.9 or 3.0 N / mm.

17. A flexible copper-clad laminate comprising the polyester electronic adhesive as described in any one of claims 14-16.

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