WO2016108490A1 - Acide de polyamide thermoplastique hydrosoluble réticulé et son procédé de fabrication - Google Patents

Acide de polyamide thermoplastique hydrosoluble réticulé et son procédé de fabrication Download PDF

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WO2016108490A1
WO2016108490A1 PCT/KR2015/014076 KR2015014076W WO2016108490A1 WO 2016108490 A1 WO2016108490 A1 WO 2016108490A1 KR 2015014076 W KR2015014076 W KR 2015014076W WO 2016108490 A1 WO2016108490 A1 WO 2016108490A1
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polyamic acid
water
soluble thermoplastic
soluble
mol
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PCT/KR2015/014076
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English (en)
Korean (ko)
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명범영
김성원
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에스케이씨코오롱피아이 주식회사
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Priority to CN201580072133.2A priority Critical patent/CN107108887B/zh
Publication of WO2016108490A1 publication Critical patent/WO2016108490A1/fr

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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
    • 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
    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • 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
    • C08G73/1003—Preparatory processes
    • 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
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention provides a crosslinkable water-soluble thermoplastic polyamic acid that can be used in the production of a heat-sealed multilayer polyimide film for a double-sided FCCL (flexible copper clad laminate) interlayer insulating material and a method for producing the same.
  • FCCL flexible copper clad laminate
  • FPCs flexible printed circuit boards
  • the flexible printed wiring board is manufactured from a two-layer flexible copper clad laminate (two-layer FCCL) in which a metal layer is formed directly on a polyimide film without using a thermosetting adhesive.
  • Casting method of flexible coating of polyamic acid as a precursor, followed by imidization, (ii) Metallizing method of forming a metal layer directly on a polyimide film by sputtering, and (iii) Heat-adhesive polyimide coated with thermoplastic polyimide on both sides The lamination method which fuses a laminated film with metal foil at high temperature is known.
  • the laminating method is preferred in that the thickness of the applicable metal foil is wider than that of the casting method, and the device cost is lower than that of the metallizing method.
  • the heat-adhesive polyimide laminated film used as an essential insulating material for the lamination method includes coating a polyamic acid solution, which is a thermoplastic polyimide precursor, onto a high elastic polyimide base film, and a high temperature curing treatment for imidizing the thermoplastic polyamic acid. It is manufactured through a two step process. According to this method, the thermoplastic polyamic acid is diluted in a polar organic solvent, followed by coating and high temperature imidization process.
  • the thermoplastic polyimide coated on the polyimide base film not only shows low interfacial adhesion reliability with the base film, but also the coating Due to the cumulative residual stress generated during the drying and curing process, the dimensional stability of the film is greatly decreased, and the process cost increases.
  • Korean Patent Application No. 2014-36305 discloses an inline coating-film forming process of coating a thermoplastic polyamic acid, which is a thermoplastic polyimide precursor, on a polyimide gel film, and drying and hot curing.
  • the method requires that the thermoplastic polyamic acid not only be polymerized into a high polymer in order to secure mechanical strength and interfacial adhesion reliability, but also use a large amount of polar organic solvent as a diluent to exhibit an appropriate viscosity of 500 to 1,000 cP. It was.
  • the coating solution in which the thermoplastic polyamic acid is diluted shows a change in viscosity over time by reversible reactions such as amide exchange reaction and hydrolysis during storage at room temperature, causing problems such as deterioration of coating quality during long time coating. In order to improve this, it is difficult to secure stable coating quality due to condensation problems even when the coating solution is maintained at a low temperature by using a cold storage tank.
  • the polar organic solvent used as a diluent is highly toxic, very expensive, and there is a risk of explosion during the curing process.
  • Japanese Patent No. 4,806,836 describes an example in which a water-soluble polyimide precursor is obtained using anhydrides having sulfonic acid, but its use is limited because of its extremely low mechanical strength and impossibility of implementing heat adhesives. Japanese Patent No.
  • 5,375,597 describes an example in which an alkali metal hydroxide, an alkali metal carbonate and / or an alkali metal phosphate is reacted with a polyamic acid to obtain a water-soluble polyimide having high solubility in water, but a polyimide precursor mixed with an alkali metal hydroxide Not only the composition was difficult to high molecular weight, but also the alkali metal hydrate remained in the obtained polyimide coating layer, resulting in a decrease in heat resistance and electrical insulation and cracking.
  • Another object of the present invention is to provide a method for producing the crosslinking water-soluble thermoplastic polyamic acid.
  • Cross-linked water soluble obtained by polymerizing a diamine component comprising an acid dianhydride component and 3,5-diamino benzoic acid (DAB), followed by end modification with 4-phenylethynylphthalic anhydride (PEPA) and reacting with a water soluble amine.
  • DAB 3,5-diamino benzoic acid
  • PEPA 4-phenylethynylphthalic anhydride
  • Adding a 4-phenylethynylphthalic anhydride and a water-soluble amine to a polyamic acid solution prepared by polymerizing a diamine component including an acid dianhydride component and a 3,5-diamino benzoic acid in an organic solvent, followed by reacting Provided is a method for producing a crosslinking water-soluble thermoplastic polyamic acid.
  • the cross-linked water-soluble thermoplastic polyamic acid according to the present invention may be coated using water as a diluent instead of expensive toxic organic solvents, and may be inline coated safely, environmentally and economically without risk of explosion due to vapor.
  • the present invention is obtained by polymerizing a diamine component comprising an acid dianhydride component and 3,5-diamino benzoic acid (DAB), followed by end modification with 4-phenylethynylphthalic anhydride (PEPA) and reacting with a water-soluble amine, It provides a crosslinking water-soluble thermoplastic polyamic acid.
  • DAB 3,5-diamino benzoic acid
  • PEPA 4-phenylethynylphthalic anhydride
  • the water-soluble amine may be used at least one selected from the group consisting of N, N-dimethylethanolamine (DMEA) and trimethanolamine (TMA), preferably N, N-dimethylethanolamine (DMEA) can be used. have.
  • the viscosity of the crosslinkable water soluble thermoplastic polyamic acid of the present invention is determined by the molar ratio of total acid dianhydride and total diamine added, and is 10,000 to 50,000 cP (at 23 ° C., an aqueous solution of 30% by weight of solids), preferably 25,000 to 35,000 cP. If the viscosity is 10,000 cP or more, the molecular weight is low to prevent the mechanical strength is lowered to show a low adhesive strength, if it is 50,000 cP or less it can prevent the effect that the room temperature stability of the polyamic acid solution is lowered.
  • crosslinkable water-soluble thermoplastic polyamic acid of the present invention may have a weight average molecular weight of 10,000 to 300,000 g / mol, 20,000 to 200,000 g / mol, 30,000 to 100,000 g / mol, or 30,000 to 50,000 g / mol.
  • the crosslinking water-soluble thermoplastic polyamic acid of the present invention is characterized by including a carboxyl group (-COOH) which is a hydrophilic functional group in the main chain.
  • the crosslinkable water-soluble thermoplastic polyamic acid of the present invention is added with water so as to be 10% by weight of an aqueous solution, and when stirred at 50 ° C. for 3 hours, it does not form precipitates or gels, thereby exhibiting excellent solubility. It was.
  • the cross-linked water-soluble thermoplastic polyamic acid in the form of an aqueous solution was left at room temperature for 12 hours, and the viscosity was measured. As a result, the drop was less than 10%, preferably 5 to 7% relative to the initial viscosity. This did not occur it was found that the storage stability is excellent.
  • the crosslinked water-soluble thermoplastic polyamic acid according to the present invention contains a carboxyl group (-COOH), which is a hydrophilic functional group, in the main chain, thereby exhibiting high compatibility with water and storage stability. Therefore, when the cross-linked water-soluble thermoplastic polyamic acid of the present invention is used as a coating liquid for implementing a heat-sealed adhesive layer when the multilayer polyimide film is manufactured, the coating is possible in an aqueous state, which is very environmentally friendly. In addition, it is possible to secure excellent mechanical strength and high interfacial adhesion by performing self cross-linking after coating.
  • -COOH carboxyl group
  • the multi-layered polyimide film prepared from the crosslinked water-soluble thermoplastic polyamic acid of the present invention is excellent in terms of heat resistance and elastic modulus as well as excellent dimensional stability, and is free from twisting, twisting and warping due to changes in temperature and other processing conditions. . Therefore, the multi-layered polyimide film prepared from the cross-linked water-soluble thermoplastic polyamic acid can be very usefully used as an interlayer insulating material for lamination (heat fusion) double-sided FCCL production.
  • the present invention is a polyamic acid solution prepared by polymerizing a diamine component containing an acid dianhydride component and 3,5-diamino benzoic acid in an organic solvent, to which 4-phenylethynylphthalic anhydride and a water-soluble amine are added. It provides a method for producing a crosslinking water-soluble thermoplastic polyamic acid, including the step of post-reacting.
  • the method for producing a crosslinkable water-soluble thermoplastic polyamic acid according to the present invention in order to achieve high adhesion and proper polymerization degree (viscosity), at least one acid dianhydride component and 3,5-diamino benzoic acid of a certain mole fraction
  • a thermoplastic polyimide precursor having a terminal sealed therein.
  • the preparation method of the present invention can be prepared according to the following Scheme 1, for example.
  • R1 and R2 are each independently ego
  • R ⁇ 1 and R ⁇ 2 are each independently ego;
  • R ⁇ 1 is CH 3 or C 2 H 5 .
  • the acid dianhydride components include 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 2,3,3', 4'-biphenyltetracarboxylic dianhydride (a-BPDA), 3 And at least one acid dianhydride component selected from the group consisting of 3'4,4'-benzophenone tetracarboxylic dianhydride (BTDA) and pyromellitic dianhydride (PMDA), preferably BPDA, BTDA or Mixtures thereof can be used.
  • BPDA 4,4'-biphenyltetracarboxylic dianhydride
  • a-BPDA 2,3,3', 4'-biphenyltetracarboxylic dianhydride
  • PMDA pyromellitic dianhydride
  • the diamine component includes 3,5-diamino benzoic acid (DAB) as an essential component, in addition to 4,4'-diaminodiphenyl ether (ODA), 4,4'-diaminobenzophenone, 4, 4'-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 1,3-bis (4-aminophenoxy) benzene (TPER), 1,3-bis (3-aminophenoxy ) Benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) diphenylether, 4,4'-bis (4-aminophenyl) diphenylmethane, 4 With 4'-bis (4-aminophenoxy) diphenyl ether, 4,4'-bis (4-aminophenoxy) diphenylmethane and 2,2-bis [4- (aminophenoxy) phenyl] propane
  • DDA 4,
  • the organic solvent may be at least one selected from the group consisting of dimethylformamide (DMF), dimethylacetamide (DMAc) and N-methylpyrrolidone (NMP), preferably N, N-dimethylacet Amide can be used.
  • DMF dimethylformamide
  • DMAc dimethylacetamide
  • NMP N-methylpyrrolidone
  • water-soluble amine one or more selected from the group consisting of N, N-dimethylethanolamine (DMEA) and trimethanolamine (TMA) may be used, and preferably N, N-dimethylethanolamine (DMEA) may be used. Can be.
  • DMEA N-dimethylethanolamine
  • TMA trimethanolamine
  • the content of the essential diamine component 3,5-diamino benzoic acid may be 3 mol% to 10 mol%, preferably 3 mol% to 9 mol% with respect to the total diamine component.
  • the content of DAB is 3 mol% or more, there is no problem of deterioration in compatibility, and thus the room temperature storage stability of the coating solution containing the crosslinkable water-soluble thermoplastic polyamic acid may be improved.
  • the content is 10 mol% or less, the hygroscopicity by the carboxyl hydrophilic functional group is increased. Such problems do not occur, and thus the hygroscopic high temperature reliability may be improved in manufacturing a double-sided flexible copper clad laminate (FCCL).
  • FCCL double-sided flexible copper clad laminate
  • the content of the total acid dianhydride component may be 95 mol% to 99 mol%, preferably 96 mol% to 99 mol% with respect to the content of the total diamine component.
  • the total acid dianhydride component is 95 mol% or more with respect to the total diamine component content, it is possible to prevent the decrease in strength due to the low molecular weight and to secure the copper foil and high adhesive properties during thermal fusion, and the total dianhydride component is added to the total diamine component content.
  • the content is less than 99 mol%, it is possible to prevent the formation of excessive polymer polymers, thereby to gel the polyamic acid during the polymerization process or to prevent undissolved or gelation during the preparation of the coating solution in the aqueous solution and storage, thereby ensuring excellent coating quality.
  • the content of 4-phenylethynylphthalic anhydride (PEPA) for the polymerized thermoplastic polyamic acid terminal encapsulation is such that the unreacted diamine end in the polyamic acid polymer can be encapsulated by the content of the dianhydride component and the polymerization ratio of the diamine component. It is added in an equivalent ratio, and may be 2 mol% to 11 mol%, preferably 3 mol% to 7 mol% with respect to the content of the diamine component.
  • PEPA 4-phenylethynylphthalic anhydride
  • the content of water-soluble amine preferably N, N-dimethylethanolamine (DMEA), which is reacted with the polyamic acid, is from 60 mol% to 110 mol%, preferably 70 with respect to the total acid dianhydride content. mol% to 100 mol%. If the content of the water-soluble amine is more than 60 mol% can prevent the generation of insoluble gelling, if less than 110 mol% it can prevent the decrease in coating quality and the cost increase by excessively increasing the amount of amine.
  • DMEA N, N-dimethylethanolamine
  • the viscosity of the crosslinkable water-soluble thermoplastic polyamic acid of the present invention is determined by the molar ratio of the total dianhydride added to the total diamine and is 10,000 to 50,000 cP (at 23 ° C., an aqueous solution of 30% by weight solid), preferably 25,000 to 35,000 cP.
  • the viscosity is 10,000 cP or more, the molecular weight is low to prevent the mechanical strength from dropping to show low adhesive strength.
  • the viscosity is 50,000 cP or less, the molecular weight is high to prevent the stability of the room temperature stability of the solution containing the crosslinkable water-soluble thermoplastic polyamic acid. have.
  • crosslinkable water-soluble thermoplastic polyamic acid of the present invention may have a weight average molecular weight of 10,000 to 300,000 g / mol, 20,000 to 200,000 g / mol, 30,000 to 100,000 g / mol, or 30,000 to 50,000 g / mol.
  • the cross-linked water-soluble thermoplastic polyamic acid of the present invention is added with water so as to be an aqueous solution of 10% by weight and does not form precipitates or gels when stirred at 50 ° C. for 3 hours, thereby exhibiting high solubility. It was.
  • the viscosity of the cross-linked water-soluble thermoplastic polyamic acid in the form of an aqueous solution after standing for 12 hours at room temperature was found to be less than 10%, preferably 5 to 7% relative to the initial viscosity, the precipitate or gel This did not occur it was found that the storage stability is excellent.
  • the cross-linked water-soluble thermoplastic polyamic acid according to the present invention can be prepared into a heat-sealed multilayer polyimide film by coating on a base film and then imidized.
  • the heat-sealed multilayer polyimide film is (i) a polyimide film; And (ii) a polyimide coating layer obtained from a crosslinkable water-soluble thermoplastic polyamic acid, which is formed on one or both sides of the polyimide film, wherein the crosslinkable water-soluble thermoplastic polyamic acid is formed of an acid dianhydride component and a 3,5- It is obtained by polymerizing the diamine component containing diamino benzoic acid (DAB), followed by terminal modification with 4-phenylethynylphthalic anhydride (PEPA) and reacting with a water-soluble amine.
  • DAB diamino benzoic acid
  • PEPA 4-phenylethynylphthalic anhydride
  • the heat-sealed multilayer polyimide film may include a polyimide base layer exhibiting high heat resistance and high elastic properties; And a polyimide coating layer formed on one or both surfaces of the substrate layer, preferably a polyimide substrate layer; And it may be a laminate of three layers including a polyimide coating layer formed on both sides of the base layer.
  • the heat-sealed multilayer polyimide film including the cross-linked water-soluble thermoplastic polyamic acid as a coating layer exhibits high interfacial adhesion of 1,210 to 1,560 gf / cm with respect to the copper foil due to the high compatibility between the base layer and the coating layer.
  • the heat-sealed multilayer polyimide film may be usefully used in electronic materials such as flexible wiring boards, particularly in flexible copper foil laminate (FCCL), and also in flexible printed circuit boards.
  • electronic materials such as flexible wiring boards, particularly in flexible copper foil laminate (FCCL), and also in flexible printed circuit boards.
  • FCCL flexible copper foil laminate
  • the manufacturing method of the said heat-sealed multilayer polyimide film is (1) 4-phenyl to the polyamic-acid solution produced by superposing
  • the heat-sealed multilayer polyimide film of the present invention may be prepared by a method comprising the following steps:
  • a step for preparing a water-soluble thermoplastic polyimide precursor of the present invention for implementing a heat-sealing layer wherein a predetermined molar fraction of an acid dianhydride component and a diamine component containing 3,5-diamino benzoic acid are necessary in an organic solvent. Dissolved to prepare a polyamic acid, which is end-sealed with 4-phenylethynylphthalic anhydride, and then reacted with an appropriate amount of N, N-dimethylethanolamine (DMEA) to obtain a cross-linked water-soluble thermoplastic polyamic acid, which is diluted with an appropriate amount of water. To prepare a coating solution;
  • Step (1) is a step for preparing a crosslinkable water-soluble thermoplastic polyimide precursor solution, which is a coating solution for implementing a heat-sealed adhesive layer, and is the same as the method for preparing a crosslinkable water-soluble thermoplastic polyamic acid described above.
  • crosslinkable water-soluble thermoplastic polyamic acid of the present invention as a coating liquid, water is added to the crosslinkable water-soluble thermoplastic polyamic acid (varnish) and dissolved for 2 hours while stirring at 60 ° C. to give a solid content of 5 to 10% by weight and a viscosity of 100 to 100%.
  • a coating solution of 300 cP (at 23 ° C.) may be prepared.
  • the step (2) is a step of in-line coating on one or both sides of the gel film of the polyamic acid component using the cross-linked water-soluble thermoplastic polyamic acid as a coating liquid.
  • the gel film of the polyamic acid component is used as a base film in the production of a heat-sealed multilayer polyimide film, it can be prepared according to a conventional method for producing a polyamic acid gel film known in the art. For example, (i) the gel film of the polyamic acid component to prepare a polyamic acid solution by polymerizing an acid dianhydride component and a diamine component in an organic solvent to implement a high elastic polyimide substrate layer; And (ii) mixing the polyamic acid solution with the imidization conversion solution and then casting the mixed solution onto the support.
  • Step (i) is a step of preparing a polyamic acid solution in order to implement a high elastic polyimide substrate layer, and dissolves a certain molar fraction of the acid dianhydride component and the diamine component in an organic solvent, and then polymerizes and reacts the high heat resistant high elastic polyimide substrate film. It is a step of preparing a polyamic acid solution that is a precursor of.
  • the polyamic acid which is a precursor of the high heat resistant high elastic polyimide substrate film may be prepared according to the method according to Scheme 2, for example.
  • R1 and R2 are each independently ego
  • R ⁇ 1 and R ⁇ 2 are each independently to be.
  • the polyamic acid solution is implemented as a core layer of a polyimide film exhibiting high heat resistance and high elasticity through a multilayer film forming process, and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) and pyromelli
  • BPDA 4,4'-biphenyltetracarboxylic dianhydride
  • BPDA 4,4'-biphenyltetracarboxylic dianhydride
  • BTDA 3,3'4,4'-benzophenonetetracarboxylic dianhydride
  • PDA triacid dianhydride
  • MDA 3,4'-phenylenediamine
  • the organic solvent may be at least one selected from the group consisting of dimethylformamide (DMF), dimethylacetamide (DMAc), and N-methylpyrrolidone (NMP).
  • DMF dimethylformamide
  • DMAc dimethylacetamide
  • NMP N-methylpyrrolidone
  • Step (ii) is to mix the polyamic acid solution prepared in step (i) with the imidization conversion solution and then cast the mixture on a support to prepare a gel film for implementing the core layer of the heat-sealed multilayer polyimide film Step.
  • the imidization conversion solution used in the present invention may be used as long as it is a material commonly used to cause chemical curing, and it may be a mixed solution of three kinds such as a dehydrating agent, a catalyst, and a polar organic solvent. More specifically, the imidization conversion liquid may be a dehydrating agent such as acetic dianhydride; Tertiary amine imidation catalysts such as pyridine, betapicolin and isoquinoline; And a polar organic solvent such as N-methylpyrrolidone (NMP), dimethylformamide (DMF), and dimethylacetamide (DMAc).
  • NMP N-methylpyrrolidone
  • DMF dimethylformamide
  • DMAc dimethylacetamide
  • the imidization conversion solution may be used in an amount of 30 to 70 parts by weight based on 100 parts by weight of the polyamic acid solution, but may vary depending on the type of polyamic acid solution and the thickness of the polyimide film to be produced.
  • the gel film may be prepared by casting a polyamic acid mixture on a support for 1 to 10 minutes at 70 to 180 °C, preferably 100 to 150 °C. If the temperature is 70 °C or more during casting, the gel film is easy to dry and there is no fear of productivity decrease by shortening the residence time on the support. If the temperature is below 180 °C, it is possible to prevent rapid solvent volatilization. Condensation, etc., due to the condensation of the solvent do not occur.
  • the gel film produced by casting on the support may have a thickness of, for example, 5 to 100 ⁇ m, preferably 20 to 100 ⁇ m, depending on the discharge amount of the polyamic acid mixture when the residual solvent amount is 20 to 30 wt%. If the thickness of the gel film is 5 ⁇ m or more, the gel film does not have a deterioration in self-support and is easy to handle. If the thickness of the gel film is 100 ⁇ m or less, an increase in the amount of volatile solvent can be prevented, thereby reducing the productivity. Considering the thickness of a commercially available multilayered polyimide film, the residual solvent amount may be about 20% by weight and the thickness of the gel film may be 7 to 55 ⁇ m.
  • the substrate layer After drying, the substrate layer has a thickness of 5 to 45 ⁇ m in the multilayer film, and is subsequently coated with a crosslinking water-soluble thermoplastic polyamic acid with a coating solution and inline-coated to one or both sides of the substrate layer to heat-seal the final thickness of 9 to 50 ⁇ m.
  • Multilayer polyimide films can be produced.
  • one or both surfaces of the gel film of the polyamic acid component may be inline coated using an inline coater with the water-soluble thermoplastic polyamic acid coating liquid prepared in step (1).
  • in-line coating refers to the coating of a thermoplastic polyimide precursor solution, unlike an off-line coating, that is, a process of coating a polyimide or a precursor solution thereof on the surface of a substrate based on an imidized heat-resistant polyimide film. It means what consists of together in the base material manufacturing process of this polyimide.
  • a process of coating a cross-linked water-soluble thermoplastic polyimide coating solution on one or both surfaces of a semi-dry gel film produced during the manufacturing process of a polyimide film using an inline coater, and simultaneously coating both sides simultaneously or one side can be coated sequentially.
  • the viscosity of the crosslinkable water-soluble thermoplastic polyamic acid coating liquid may be 200 to 1,000 cP, preferably 300 to 800 cP or less, and more preferably 500 to 700 cP (based on 23 ° C.). Water may be used as a diluent for the desired viscosity to adjust the solids content of the crosslinkable water-soluble thermoplastic polyamic acid coating solution to 5 to 10% by weight to have an appropriate viscosity as described above.
  • the viscosity of the polyamic acid coating liquid is 200 cP or more, it is possible to prevent staining due to excessive flow of the coating liquid during coating, and does not cause a problem that the thickness of the mechanical direction (MD, Mechanical Direction) is uneven. It is possible to prevent the die line generation due to the decrease in flatness and does not cause the problem of non-uniform thickness of the transverse direction (TD).
  • the coating thickness of the polyamic acid coating solution may be 15 to 70 ⁇ m, preferably 20 to 40 ⁇ m when the coating is performed by adjusting the content of solids in the coating solution to 10 wt%. If the thickness is 15 ⁇ m or more, the thickness of the polyimide coating layer after drying may be appropriate to express sufficient adhesion with copper foil during the high temperature roll lamination process for manufacturing double-sided FCCL. It does not cause excessive melting during the hot roll lamination process, and does not cause degradation in adhesion without generating polyimide skid marks on the FCCL appearance.
  • the thickness of the crosslinkable water-soluble thermoplastic polyamic acid coating layer may be 1.5 to 7 ⁇ m after drying, and the final thickness after drying of the heat-sealed multilayer polyimide film including the coating layer may be 12 to 50 ⁇ m.
  • Step (3) is a step of imidizing the gel film having a crosslinkable water-soluble thermoplastic polyamic acid coating layer on one or both surfaces at high temperature.
  • the imidation may be performed by slowly heating at a temperature of 200 to 500 ° C. for 1 to 30 minutes. If the imidization temperature is 200 ° C. or more, the imidization rate may be appropriate to obtain a sufficiently imidized multilayer film. If it is lower than or equal to C, there is no fear of carbon water or bubble generation due to the temperature rise. In addition, if the imidization time is in the range of 1 to 30 minutes, sufficient imidization is achieved and there is no fear of deterioration of physical properties due to film degradation.
  • a cross-linked water-soluble thermoplastic polyamic acid coating solution is coated on a semi-drying gel layer, which is a semi-dry substrate layer, thereby improving interlayer interfacial adhesion of the multilayer polyimide film and simultaneously forming a film-coating process. This greatly improves the dimensional stability of the multilayer polyimide film.
  • the manufacturing method of the present invention unlike the existing off-line coating method can be produced in-line multi-layer film during the polyimide film forming process it is possible to innovatively lower the manufacturing cost.
  • the in-line double-side coating machine used in the present invention can effectively control coating defects by preventing vibration and vibration generated during the driving process for drying the gel film, as well as mounting a two-head double-side coating equipment in a narrow space. This enables efficient utilization of existing polyimide film production equipment.
  • the present invention it is possible to produce high quality heat-sealed multilayer polyimide film in an environmentally friendly, safe and economical manner.
  • the heat-sealed multilayer polyimide film is obtained by in-line coating a crosslinkable water-soluble thermoplastic polyamic acid coating solution on one side or both sides of a high elastic polyimide gel film, so there is no risk of explosion due to coating solvent vapor during drying and high temperature curing.
  • thermoplastic polyamic acid (varnish) was prepared, which was a thermoplastic polyimide precursor having a rotational viscosity at 23 ° C. of 31,000 cP.
  • the molar ratio of the acid dianhydride and diamine of the polyamic acid was adjusted to 0.983: 1, and the weight average molecular weight was predicted to be Mn 30,000 g / mol by the equivalent ratio of equivalents.
  • the 4'-diaminodiphenylether solution was added in small portions until the target viscosity was reached, followed by stirring polymerization at a rotational speed of 50 rpm at 40 ° C. to obtain a solid content of 18.5 wt% and a heat resistance of 350,000 cP at 23 ° C.
  • the polyamic acid solution which is a polyimide precursor was obtained.
  • the weight average molecular weight of the heat resistant polyimide precursor is predicted to be Mn 300,000 g / mol by the equivalent ratio of the equivalents.
  • the heat resistant polyamic acid solution prepared in the above 1-2 was mixed with the imidization conversion solution, but the mixing ratio of the heat resistant polyamic acid solution and the imidization conversion solution was 100: 40 by weight.
  • the imidization conversion solution is composed of a dehydrating agent, a catalyst, and a polar organic solvent, and the composition and dosage of each component are as follows.
  • (A) Dehydrating agent 2.0 mol of acetic dianhydride is used with respect to 1 mol of amic-acid units of a heat resistant polyamic-acid solution.
  • (C) Polar organic solvent 3 mol of DMF solution is used with respect to 1 mol of amic-acid units of a heat resistant polyamic-acid solution.
  • a mixture of the heat resistant polyamic acid solution and the imidization conversion solution was introduced at a rate of 13.83 kg / hr into a flow path of an extrusion die having a lip width of 740 mm and a lip spacing of 1.0 mm.
  • An extrudate film of the mixture extruded from the lip of the extrusion die was cast on an endless casting belt warmed to 130 ° C. to produce a gel film having a uniform thickness.
  • the endless casting belt was rotated at a speed of 2.5 m / min to allow the gel film to stay on the heated endless casting belt for 180 seconds.
  • the thickness of the gel film was 35 ⁇ m.
  • the cross-linked water-soluble thermoplastic polyamic acid coating liquid of Example 1-1 was coated on both sides of the gel film through an in-line coating equipment.
  • the viscosity of the crosslinkable water-soluble thermoplastic polyamic acid coating solution is 200 cP (23 ° C. standard), and the solid content of the crosslinkable water-soluble thermoplastic polyamic acid coating solution of Example 1-1 is 5 to 10% by weight using water as a diluting solvent. It was adjusted to have the desired viscosity.
  • thermoplastic polyimide precursor coating Both ends were fixed with fixing pins to transfer the gel film coated with the thermoplastic polyimide precursor coating for drying and high temperature curing of the coating solution.
  • a two-head double side coater used for inline double side coating for example, had a top of a die coating structure including a slot die and a bottom of a gravure coating structure including a gravure coating roll.
  • the thickness of the polyamic acid coating layer formed on one surface and the rear surface of the gel film was adjusted to have a final thickness of 2.5 ⁇ m after drying.
  • thermoplastic polyimide coating layer was depinned and wound by heating and imidizing a double coated gel film having both ends fixed with pins at a speed of 2.5 m / min for 300 ° C ⁇ 16 seconds, 400 ° C ⁇ 29 seconds, and 450 ° C ⁇ 17 seconds.
  • a three-layer polyimide film (heat-sealed multilayer polyimide film) consisting of a heat resistant polyimide layer and a thermoplastic polyimide coating layer was prepared.
  • the thermoplastic polyimide coating layer, the heat resistant polyimide layer and the thermoplastic polyimide coating layer were each 600 mm in width, and their thicknesses were 2.5 ⁇ m, 15 ⁇ m, and 2.5 ⁇ m, respectively.
  • a three-layer polyimide film was prepared in the same manner as in Example 1, except that the composition of the crosslinkable water-soluble thermoplastic polyimide coating solution was changed as shown in Table 1 below.
  • the molar ratio of the acid dianhydride and diamine of the crosslinkable water-soluble thermoplastic polyamic acid was adjusted to 0.999: 1
  • Table 1 A three-layer polyimide film was prepared in the same manner as in Example 1, except that the composition of the crosslinkable water-soluble thermoplastic polyimide coating liquid was changed as described in.
  • the weight average molecular weight of the crosslinking water-soluble thermoplastic polyamic acid of Comparative Examples 1-1 and 1-2 is estimated to be 400,000 g / mol and 500,000 g / mol, respectively, by the equivalent ratio of the equivalents.
  • a three-layer polyimide film was prepared in the same manner as in Example 1 using the composition of the crosslinking water-soluble thermoplastic polyamic acid coating solution described in Table 1 below.
  • a polyimide gel film was prepared in the same manner as in Example 1-2, and the polyimide film was heated and imidized for 300 ° C. ⁇ 16 seconds, 400 ° C. ⁇ 29 seconds, 450 ° C. ⁇ 17 seconds without an inline coating process. Prepared. Thereafter, a three-layer polyimide film was prepared by coating a crosslinkable water-soluble thermoplastic polyamic acid on both sides of the polyimide film using an offline coating machine.
  • the coating solution was the same crosslinking type water-soluble thermoplastic polyamic acid coating solution as in Examples 1, 2 or 3, respectively, and dried for 1 minute at 150 ° C for curing of the crosslinking type water-soluble thermoplastic polyamic acid coated on both sides, followed by curing at 300 ° C. Heat treatment was performed for 1 minute at.
  • the cross-linked water-soluble aqueous thermoplastic polyamic acid solution (solid content of 10% by weight) was left at room temperature for 12 hours, and the viscosity was measured, and the viscosity drop was greater than 10% relative to the initial viscosity, or when no precipitate or gel generation was observed, the process was incompatible (NG).
  • the composition of the crosslinkable water-soluble thermoplastic polyamic acid coating liquid was changed, and the composition of the heat-resistant polyimide gel film used as the coating substrate of the polyamic acid coating liquid was 86 mol% PPD, ODA to 100 mol% BPDA. Fixed at 14 mol%.
  • Comparative Examples 1-1 and 1-2 did not obtain satisfactory results in solubility and storage stability with a molecular weight of 400,000 to 500,000 g / mol of the crosslinkable water-soluble thermoplastic polyamic acid.
  • Comparative Examples 1-3 to 1-6 using 2-methylimidazole (DMZ) or triethylamine (TEA) instead of dimethylethanolamine (DMEA) as the amine compound for the preparation of the cross-linked water-soluble thermoplastic polyamic acid are water-soluble. It was found that the quality of storage after storage and thermal fusion were relatively poor.
  • Comparative Examples 2-1 to 2-5 which do not contain 4-phenylethynylphthalic anhydride (PEPA) in the water-soluble polyamic acid polymerization composition, are unable to polymerize through post-crosslinking, and are satisfactory heat-sealing interface adhesive strength when manufacturing double-sided FCCL. Can not be secured.
  • PEPA 4-phenylethynylphthalic anhydride
  • Comparative Examples 3-2 and 3-3 which do not contain DAB and PEPA, showed poor storage stability, and in particular, Comparative Examples 3-3, which did not include DAB, PEPA, and DMEA, showed both poor solubility and storage stability.
  • the thermal expansion coefficient was measured using the thermal expansion coefficient measuring apparatus (TMA 2940, TA company) on condition of the following.
  • the film thus produced was dried at 150 ° C. for 30 minutes to measure its weight, and the weight at this time was referred to as W1. Thereafter, after immersing in distilled water for 24 hours, the water droplets on the surface were wiped and weighed again, and the weight at this time was called W2.
  • the moisture absorption rate was measured by the following formula from W1 and W2.
  • Hygroscopicity (%) (W2-W1) / W1 ⁇ 100
  • Tensile properties ie tensile strength, elongation and modulus, were measured according to ASTM D882.
  • the thermal contraction rate was calculated
  • Film sample 15 cm (TD: width direction of film) x 25 cm (MD: length direction of film)
  • -TD1, TD2, MD1 and MD2 lengths of the four sides of the film after being left for 24 hours at an ambient temperature of 20 ° C. and a relative humidity of 60% Rh.
  • TD1 ', TD2', MD1 'and MD2' After measuring TD1, TD2, MD1 and MD2, cover the film with aluminum foil and ensure that the films do not overlap, then heat the film at 300 ° C for 2 hours After heating, the film was placed in a chamber at 20 ° C. and a relative humidity of 60% Rh for 30 minutes, and the length of the four sides of the film was measured.
  • Example 1 ⁇ 18.3 3.1 35 60 590 -0.04 ⁇ ⁇ 1320
  • Example 2 ⁇ 18.2 3.2 40 65 620 -0.03 ⁇ ⁇ 1400
  • Example 3 ⁇ 19.0 3.5
  • Example 4 ⁇ 18.4 3.8 30 63 580 -0.04 ⁇ X 1430
  • Example 5 ⁇ 18.4 3.9 35 62 560 -0.03 X X 1460
  • Example 6 ⁇ 19.3 3.2 38 69 610 -0.04 ⁇ ⁇ 1310
  • Example 7 ⁇ 19.8 3.2 36 62 610 -0.08 ⁇ ⁇ 1340
  • Example 8 ⁇ 19.4
  • the heat-sealed multilayer polyimide film of Examples 1 to 10 of the present invention is not only excellent in appearance quality after coating due to the excellent aqueous solution property of the crosslinking water-soluble thermoplastic polyamic acid, but also heat resistance and moisture absorption rate.
  • the results also showed good results in evaluation of the hygroscopic expansion coefficient and mechanical strength.
  • the moisture absorption heat resistance characteristics were deteriorated due to the increase in the content of the carboxyl functional group, which is a hydrophilic functional group, with the increase of the DAB molar ratio.
  • the films of Examples 1 to 10 were significantly higher in interfacial adhesion between the base layer and the coating layer and lower in thermal shrinkage (higher dimensional stability) than in the offline coating films of Comparative Examples 4-1 to 4-3. appear.
  • Comparative Examples 2-1 to 2-5 which do not include PEPA for terminal crosslinking in the water-soluble polyamic acid polymerization composition, are not polymerizable through post-crosslinking, thereby ensuring satisfactory heat-sealing interface adhesion in the production of double-sided FCCL. There was no. Furthermore, in Comparative Example 3-3, the formation of the coating layer was not possible due to the generation of a large amount of water-soluble gels.

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Abstract

La présente invention concerne un acide de polyamide thermoplastique hydrosoluble réticulé qui peut être utilisé dans la préparation d'un film de polyimide multicouche à thermo-soudage pour un matériau d'isolation intercouche d'un stratifié double face gainé en cuivre souple (FCCL), et son procédé de préparation. L'acide de polyamide thermoplastique hydrosoluble réticulé selon la présente invention peut être revêtu au moyen de l'eau en tant que solvant de dilution, au lieu de solvants organiques toxiques coûteux, et peut donc être revêtu en ligne de manière sécurisée, et sans danger pour l'environnement, de manière économique, sans risque d'explosion provoquée par brouillard d'huile.
PCT/KR2015/014076 2014-12-30 2015-12-22 Acide de polyamide thermoplastique hydrosoluble réticulé et son procédé de fabrication WO2016108490A1 (fr)

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KR102213893B1 (ko) * 2019-05-08 2021-02-08 피아이첨단소재 주식회사 폴리이미드 필름 제조방법 및 이에 의해 제조된 폴리이미드 필름
KR102346581B1 (ko) * 2019-11-22 2022-01-05 피아이첨단소재 주식회사 폴리이미드 필름의 제조 방법 및 이에 의해 제조된 폴리이미드 필름
CN114685787B (zh) * 2020-12-27 2024-03-08 上海市塑料研究所有限公司 一种具有协同交联结构的聚酰亚胺薄膜及其制备方法和应用
CN114920932B (zh) * 2022-06-06 2023-08-22 黑龙江省科学院石油化学研究院 一种稳定性良好、耐高温热固性聚酰亚胺前驱体溶液及制备方法
CN116145428A (zh) * 2022-12-05 2023-05-23 东华大学 一种水溶性聚酰胺酸盐上浆剂的制备方法和应用

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