WO2018216853A1 - 레이저 박리 용이성 및 고내열성을 갖는 폴리아믹산 수지의 제조방법 및 이를 이용하여 제조한 폴리이미드 필름 - Google Patents

레이저 박리 용이성 및 고내열성을 갖는 폴리아믹산 수지의 제조방법 및 이를 이용하여 제조한 폴리이미드 필름 Download PDF

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WO2018216853A1
WO2018216853A1 PCT/KR2017/008493 KR2017008493W WO2018216853A1 WO 2018216853 A1 WO2018216853 A1 WO 2018216853A1 KR 2017008493 W KR2017008493 W KR 2017008493W WO 2018216853 A1 WO2018216853 A1 WO 2018216853A1
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polyamic acid
acid resin
film
viscosity
diamine
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PCT/KR2017/008493
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English (en)
French (fr)
Korean (ko)
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강진수
김진모
안용호
한승진
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주식회사 대림코퍼레이션
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Priority to CN201780091107.3A priority Critical patent/CN110892002B/zh
Priority to JP2019565210A priority patent/JP6947848B2/ja
Publication of WO2018216853A1 publication Critical patent/WO2018216853A1/ko

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
    • C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
    • 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
    • C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Definitions

  • the present invention relates to a method for preparing a polyamic acid resin having easy laser peeling and high heat resistance, and a polyimide film prepared by using the polyamide resin prepared by the present invention.
  • Laser peeling is possible at low energy to produce a polyamic acid resin that can be peeled off without damage to the thin film (curl, defect, breakage, etc.) and has high heat resistance. It may be usefully used for a flexible display substrate material and a semiconductor material.
  • Flexible polymer materials are attracting attention as substrate materials of flexible displays, which are being spotlighted as next generation display devices.
  • the flexible device generally uses an organic light emitting diode (OLED) display, and a TFT process with a high process temperature (300 to 500 ° C) is used.
  • OLED organic light emitting diode
  • a TFT process with a high process temperature 300 to 500 ° C
  • Polymer materials that withstand such high process temperatures are extremely limited, and polyimide (PI) resin, which is a polymer having excellent heat resistance, is mainly used.
  • An organic light emitting diode (OLED) display manufactures a display by coating a resin on a glass substrate, thermosetting and filming the film, and removing the glass substrate from the glass substrate after several steps.
  • the viscosity of the resin in the process of applying the resin to the glass substrate during the manufacturing process is a very important factor in the film production. If the viscosity is too high, it is not easy to remove the solvent of the resin during the heat treatment, thereby deteriorating the properties of the thin film, or difficult to apply uniformly during coating, resulting in poor uniformity of the thin film, which causes product defects in OLED panel manufacturing. On the other hand, if the viscosity is too low, it is difficult to coat the thickness required for coating, and likewise, it is difficult to control the uniformity of the thin film.
  • resin having an appropriate viscosity is advantageous in thin film production.
  • product defects may occur due to thermal shock caused by high process temperatures (> 350 ° C.) during the TFT process.
  • the thin film is peeled off from the glass substrate by the laser peeling method after the thin film is manufactured.
  • the adhesive property with the glass is high after heat treatment due to the characteristics of the resin. ), Product damage, etc. occurs.
  • peeling is not easy, and if the energy is irradiated with high energy, the film is damaged.
  • Korean Patent Laid-Open Publication No. 1998-015679 relates to a method for producing an aromatic polyimide film, wherein an excessive amount of acid dianhydride is added to the aromatic diamine several times and polymerized at a temperature of about 5 to 20 ° C. using an organic polar solvent.
  • the polyimide film is made of the polyamic acid resin obtained from the resin, and thus the physical properties such as heat resistance are excellent, but the polyamic acid viscosity at room temperature is lowered while maintaining the physical properties. There is a limit in that an additional process for lowering the required amount is required.
  • the present inventors have optimized and controlled the dosing method, the split dosing time, and the polymerization temperature conditions of the composition used in the production of polyamide resin, in order to develop a polyamic acid resin having high heat resistance and easy laser peeling.
  • the molar ratio of the composition used in excess can be minimized and the viscosity can be easily adjusted, and the superior physical property properties are minimized because the molar ratio of the composition used is minimized compared to the existing method based on the equivalent level of viscosity.
  • the polyamic acid resin having the present invention can be prepared to complete the present invention.
  • an object of the present invention is to provide a method for producing a polyamic acid resin having easy laser peeling and high heat resistance.
  • the present invention is a film prepared by heat-treating the polyamic acid resin obtained by the above method, the adhesive strength of 0.2 ⁇ 2.0 N / cm, peeling energy 200mJ / cm 2 based on the film thickness 10 ⁇ 15 ⁇ m
  • the object is to provide a polyimide resin film characterized in that the thermal expansion coefficient in the range of 100 ⁇ 350 °C is 10 ppm / °C or less.
  • the present invention is a method for producing a polyamic acid resin prepared by polymerizing a composition comprising a diamine monomer, an acid dianhydride compound, and an organic solvent, wherein the polyamic acid resin is an acid dianhydride after dissolving the diamine monomer in an organic solvent.
  • the compound is polymerized by four times or more dividedly injected, but the addition time is 30 to 60 minutes intervals are provided to provide a method for producing a polyamic acid resin having easy laser peeling and high heat resistance characterized in that the input.
  • the present invention is a film prepared by heat-treating the polyamic acid resin prepared by the above method, the adhesive strength of 0.2 ⁇ 2.0 N / cm, peeling energy 200 mJ / cm 2 based on the film thickness 10 ⁇ 15 ⁇ m
  • the polyimide resin film which has a thermal expansion coefficient of 10 ppm / degrees C or less in 100-350 degreeC range is provided.
  • the polyimide resin prepared by the manufacturing method according to the present invention has a low viscosity and exhibits excellent laser peel force at low energy when producing a polyimide film through heat curing, and has excellent mechanical and heat resistance characteristics, thereby providing a flexible display substrate. It can be usefully used for materials, semiconductor materials and the like.
  • Figure 1 shows the change in viscosity according to the split input conditions when producing a polyamic acid resin according to the present invention.
  • Figure 2 is a result of testing the peeling of the film after irradiating a laser with a different energy size for the polyamide film prepared by applying a polyamic acid resin according to the present invention on a glass substrate and heat treatment (photo).
  • the present invention provides a method for producing a polyamic acid resin prepared by polymerizing a composition comprising a diamine monomer, an acid dianhydride compound, and an organic solvent.
  • a polyimide film having a low viscosity and having appropriate laser peeling properties, excellent heat resistance, and a low coefficient of thermal expansion during film production.
  • the polyamic acid resin production method according to the present invention is polymerized by dissolving the diamine monomer in an organic solvent and then divided into four or more acid dianhydride compounds, the input time is put at intervals of 30 to 60 minutes Manufacture.
  • Figure 1 shows the change in viscosity according to the split input conditions when producing a polyamic acid resin according to the present invention.
  • the viscosity of the polyamic acid resin it is preferable to add an excess of a molar ratio of the dianhydride monomer and the diamine monomer so that either side is -5 to 5 mol% to reach the target viscosity. This is for reasons of ensuring control and storage stability. However, if the molar ratio is excessively excessive on either side, it causes various properties during polyimide film production.
  • the preparation of the polyamic acid resin of the present invention by optimizing the number of times, the addition time and the polymerization temperature of the monomer, by minimizing the excess of the molar ratio of the composition to be used and adjusting the viscosity, on the basis of equivalent viscosity
  • the conventional method since it minimizes the molar ratio, it is possible to manufacture a polyamic acid resin having more excellent properties.
  • a polyamic acid resin having a low viscosity can be obtained without deteriorating physical properties.
  • the polymerization temperature is preferably 40 ⁇ 60 °C. More preferably, it is 40 degreeC.
  • dianhydride-based monomer When based on 100 mol% dianhydride-based monomer, it is preferable to add a 4 to 6 equally divided at a time difference of 30 to 60 minutes. After 4 to 6 times, the amount of the dianhydride-based monomer is adjusted according to the target viscosity of the polyamic acid solution.
  • This split-injection method enables the growth of molecular chains in the form of oligomers at an appropriate molecular weight level, not high molecular weight, to achieve viscosity in solution, and heat-treat oligomer-type molecules in high molecular weight during imidization during polyimide film production by heat treatment. Combination is possible.
  • the polyamic acid resin of the present invention may exhibit excellent mechanical properties, high heat resistance, and low coefficient of thermal expansion when manufactured into a film while having a low viscosity. This can be confirmed through an experimental example to be described later.
  • the composition used is as follows.
  • the diamine monomers which are the basic components include fluorinated aromatic diamines and non-fluorinated diamines.
  • the fluorine substituent increases the surface tension and lowers the adhesion to the glass substrate.
  • the curl, product defect, Problems such as product breakage can be improved, and excellent laser stripping characteristics can be exhibited at low energy.
  • the fluorinated aromatic diamine used in the present invention is not particularly limited as long as it is an aromatic diamine containing fluorine.
  • 2,2'-bis (trifluoromethyl) -5,5'-diaminobiphenyl (2,2'- Bis (trifluoromethyl) -5,5'-Diaminobiphenyl) but is not limited there
  • the content of such fluorinated aromatic diamine is not particularly limited, when the total diamine-based compound is 5 to 50 mol%, preferably 5 to 30 mol% based on 100 mol%, the peeling property can be expressed while maintaining the heat resistance. Can be.
  • the polyamic acid resin of the present invention may further include a non-fluorinated aromatic diamine as the aromatic diamine component.
  • a non-fluorinated aromatic diamine examples are para-phenylenediamine (PPD), meta-phenylene diamine (MPD), 4,4'-oxydianiline (ODA), bis amino phenoxy phenylpropane (6HMDA), 4,4'-diaminodi Phenyl sulfone (4,4'-DDS), 9,9'-bis (4-aminophenyl) fluorene (FDA), para-xylylenediamine (p-XDA), meta-xylylenediamine (m-XDA) , 4,4'-methylene dianiline (MDA), 4,4'-diaminobenzoate (4,4'-DABA), 4,4'-bis (4-aminophenoxy) biphenyl (4.4'- BAPP), and these may be used alone or in combination of two or more thereof.
  • non-fluorinated aromatic diamine is not particularly limited, but may be about 50 to 95 mol%, preferably 70 to 95 mol% based on 100 mol% of the diamine-based compound.
  • the polyamic acid resin of this invention contains an aromatic acid dianhydride compound as an acid dianhydride component.
  • the aromatic acid dianhydride compound when used, the polyimide heat resistance property and the low coefficient of thermal expansion can be improved. Due to the rigid molecular structure of the aromatic acid dianhydride, it is possible to produce a polyimide film having excellent heat resistance.
  • the aromatic acid dianhydride is not particularly limited.
  • 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 4,4'-(4,4'-hexafluoroisopropylidenediphenoxy) bis- (phthalic anhydride ) (6-FDPDA), pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 3,3', 4,4'-benzophenone Tetracarboxylic dianhydride (BTDA), 4,4'oxydiphthalic anhydride (ODPA), 2,2-bis [4-3,4-dicarboxyphenoxy] phenyl] propane anhydride (BPADA), 3, 3 ', 4, 4'- diphenyl sulfone tetra carboxylic anhydride (DSDA), ethylene glycol bis (4- trimellitate anhydride) (TMEG) and the like, but is not limited thereto.
  • TMEG ethylene glycol bis (4
  • the content of the aromatic acid dianhydride described above is not particularly limited, when the BPDA is 50 to 90 mol%, preferably 70 to 100 mol%, based on 100 mol% of the total acid dianhydride, PMDA 10 to 50 mol%, preferably 0 To 30 mol% may exhibit excellent heat resistance.
  • a solvent used for polyamic-acid resin manufacture of this invention if a polyamic-acid resin melt
  • NMP N-methyl-2-pyrrolidone
  • NEP N-ethyl-2-pyrrolidone
  • polar solvents such as, N-dimethyl propanamide (DMPA), low boiling solvents such as tetrahydrofuran (THF), chloroform and the like or low absorbing solvents such as gamma-butyrolactone and GBL.
  • polar solvents such as, N-dimethyl propanamide (DMPA), low boiling solvents such as tetra
  • the polyamic acid resin of the present invention may further include one or more reaction catalysts from the group consisting of trimethylamine, xylene, pyridine, and quinoline, depending on the reactivity. It is not limited.
  • the polyamic acid resin may contain a small amount of one or more additives selected from the group consisting of plasticizers, antioxidants, flame retardants, dispersants, viscosity modifiers, and leveling agents, if necessary, within a range that does not significantly impair the objects and effects of the present invention. It may include.
  • the content of aromatic diamine (B), aromatic acid dianhydride (C), organic solvent (D), and catalyst (E) is not particularly limited.
  • the total amount of an acid dianhydride component and a diamine component is 5 mass% or more, Preferably it is 10 mass% or more with respect to the total amount of a solvent, an acid dianhydride component, and a diamine component containing the polyamic-acid resin and a solvent of this invention.
  • it is the ratio of 15 mass% or more.
  • the reaction is preferably performed for 8 to 24 hours at 10 ⁇ 70 °C temperature conditions by mixing the diamine monomer 95 ⁇ 100 mol% and dianhydride monomer 100 ⁇ 105 mol% under the organic solvent conditions.
  • the dianhydride-based monomer is preferably added in an excess of -5 to 5 mol% relative to the diamine-based monomer to reach the target viscosity, for reasons of proper viscosity control and storage stability.
  • the reaction time is less than 4 hours, there is a limit in terms of storage stability of the polyamic acid resin, and in the case of more than 24 hours, there is a limit in terms of productivity.
  • the polyamic acid resin produced through this reaction preferably has a viscosity in the range of 1,000 to 7,000 cP. If the viscosity is less than 1,000 cP, there is a problem in obtaining an appropriate level of film thickness, and if it is more than 7,000 cP, there is a problem in uniform coating and effective solvent removal, so it is preferable to be within the above range.
  • the production method of the polyimide film in the present invention is as follows.
  • the present invention provides a polyimide film prepared by thermal imidating the polyamic acid resin described above.
  • the polyamic acid resin according to the present invention is viscous, and is prepared by coating and heat-treating the glass substrate in a suitable manner during film production.
  • the coating method may be used without limitation to known conventional methods, for example, spin coating (dip coating), dip coating (Dip coating), solvent casting (Solvent casting), slot die coating, spray coating (Spray coating) ), But is not limited thereto.
  • the polyamic acid resin of the present invention may be prepared into a polyimide film by heat treatment in a high temperature convection oven. At this time, the heat treatment is carried out under a nitrogen atmosphere, it is carried out for 60 to 300 minutes at 100 ⁇ 500 °C conditions. More preferably, the film is obtained under temperature and time conditions of 100 ° C./30 min, 150 ° C./10 min, 300 ° C./15 mim, and 500 ° C./10 min. This is because of the imidization which can maximize the removal of the proper solvent and properties.
  • the transparent polyimide film of the present invention is produced using the polyamic acid resin, it exhibits high transparency and has a low coefficient of thermal expansion.
  • the polyimide film of the present invention has a film thickness of 10 to 15 ⁇ m, an adhesive force of 0.2 to 2.0 N / cm, and a peeling energy of 200 mJ / cm 2.
  • the coefficient of thermal expansion in the range of 100 to 350 ° C is 10 ppm / ° C or less. Preferably lower than 5 ppm / ° C.
  • the polyimide film of the present invention can suppress defects of elements on a substrate due to curl, expansion, and shrinkage during laser peeling on a glass substrate.
  • Figure 2 is a result of testing the peeling of the film after irradiating a laser with a different energy size for the polyamide film prepared by applying a polyamic acid resin according to the present invention on a glass substrate and heat treatment (photo). But even when a laser beam of low-energy (160 mJ / cm 2) well polyimide separation, the higher the laser of an energy irradiation (220mJ / cm 2) The polyimide film of the above organic substrate is showing a phenomenon of damage have.
  • the polyimide film of the present invention can be used in various fields, and is flexible such as OLED display, liquid crystal display, TFT substrate, flexible printed circuit board, flexible OLED surface lighting substrate, and substrate material for electronic paper. ) May be provided as a display substrate and a protective film.
  • reaction temperature 23 DEG C, at which time the solid content was maintained to be 15% by weight relative to the total weight of the reaction solvent.
  • the viscosity was 5,900 cP as measured by a viscometer (Brookfield DV2T, SC4-27).
  • a polyamic acid resin was prepared in the same manner as in Comparative Example 1, except that the number of acid dianhydrides (Table 2 to 3), the addition time (30 minutes), and the excess molar ratio of diamine were used.
  • a polyamic acid resin was prepared in the same manner as in Comparative Example 1, except that the number of times of the acid dianhydride (4 to 6 times), the addition time (30 minutes), and the excess molar ratio of the diamine was used.
  • the polyamic acid resins of Comparative Examples and Examples were coated on a glass plate using a bar coater, and then heat-treated in a high temperature convection oven.
  • the heat treatment conditions were carried out in a nitrogen atmosphere, and the final film was obtained at temperature and time conditions of 100 ° C / 30min, 150 ° C / 10min, 300 ° C / 15min, and 500 ° C / 10min.
  • the film thus obtained was measured in the physical properties as shown below and the results are shown in Table 1 below.
  • the film was cut into 25mm width, and then subjected to a 90 ° peel test at a speed of 300 mm / min using Instron's UTM.
  • the coefficient of thermal expansion (CTE) of the film was measured using TMA 402 F3 from Netzsch. Force in the tension mode was set to 0.05 N, and the measured temperature was elevated to 500 ° C. at a rate of 5 / min at 30 ° C., and the coefficient of thermal expansion was measured as an average value in the range of 100 to 350 ° C.
  • T d Pyrolysis temperature
  • Instron's UTM was used to measure the mechanical properties of the film.
  • the film specimen was measured while pulling the specimen at a speed of 50 mm / min with a width of 10 mm and a gap between the grips set to 100 mm.
  • Example 2 in which the acid dianhydride was equally divided into five portions of the composition having the same level of viscosity, the heat resistance characteristics, Td (%) and CTE acid dianhydride after holding for 3 hours at 460 ° C It was found to be superior to Comparative Examples 1 to 3 in which water was added 1 to 3 times and equally divided, and to Examples 1 and 3, which were equally divided into 4 times and 6 times.
  • the acid dianhydride is introduced in a different way to minimize the excess molar ratio of acid dianhydride to diamine, which has the same level of viscosity but excellent results in terms of heat resistance and mechanical properties.
  • the number of divided inputs of acid dianhydride according to the present invention is appropriate 4 to 6 times, preferably divided into five times.
  • a polyamic acid resin was prepared in the same manner as in Comparative Example 4, except for the time between the divided additions of the acid dianhydride of Table 2 (20 minutes). Again, the monomers did not dissolve properly due to the short time between split inputs.
  • a polyamic acid resin was prepared in the same manner as in Comparative Example 4 except for the time between the split additions of the acid dianhydride of Table 2 below.
  • a polyimide film was prepared in the same manner as in Experimental Example 1, physical properties were measured, and the results are shown in Table 2 below.
  • the number of split feeds of acid dihydrate was fixed five times, and optimization evaluation of the time between split feeds was performed.
  • the time between the split inputs was short, so that sufficient dissolution of the acid dihydrate monomer was not achieved. Therefore, the production of a proper polyamic acid was a heap.
  • the input time between the splitting of the acid dianhydride monomer was put at intervals of 30 to 60 minutes, so that sufficient dissolution of the acid dianhydride monomer was possible and a proper polyamic acid solution was obtained. .
  • a polyamic acid resin was prepared in the same manner as in Example 1, except for the polymerization temperature of Table 3 and the excess molar ratio of the acid dianhydride monomer.
  • a polyimide film was prepared in the same manner as in Experimental Example 1, physical properties were measured, and the results are shown in Table 3 below.
  • Example 3 it was fixed at the number of times the acid dihydrate was added (5 times), the time between the inputs (30 minutes), and the optimization evaluation of the polymerization temperature was performed. Compared with Example 2-1, as shown in the results of Examples 2-5 to 2-7, as the polymerization temperature was increased, the excess molar ratio of the acid dianhydride monomer was reduced, and the heat resistance and mechanical properties were increased while showing the same level of viscosity. It can be seen. Depending on the polymerization temperature of 40 to 60 °C of Examples 2-5 to 2-7 it can be seen that the characteristics of the equivalent level.
  • Comparative Example 6 shows that the excess molar ratio of the acid dianhydride monomer is reduced at the polymerization temperature of 70 ° C., and the characteristics are inferior to those of Examples 2-5 to 2-7 even at the same level of viscosity.
  • the polymerization temperature is appropriately 40 ⁇ 60 °C, 40 °C is preferred.
  • the dianhydride-based monomer is divided into four or more times at a polymerization temperature of 40 ⁇ 60 °C, the input time is obtained by polymerization with a time difference of 30 to 60 minutes intervals
  • the film which has the ease of laser peeling and high heat resistance can be manufactured.
  • reaction temperature 60 °C / 6 hours after stirring for 25 °C, the solid content is to be maintained to 15% by weight relative to the total weight of the reaction solvent.
  • the viscosity was 6,000 cP.
  • reaction temperature 60 °C / 6 hours after stirring for 25 °C, the solid content is to be maintained to 15% by weight relative to the total weight of the reaction solvent.
  • the viscosity was 6,100 cP.
  • reaction temperature 40 °C / 6 hours after stirring for 25 °C, the solid content is to be maintained to 15% by weight relative to the total weight of the reaction solvent.
  • the viscosity was 5,800 cP.
  • reaction temperature 60 °C / 6 hours after stirring for 25 °C, the solid content is to be maintained to 15% by weight relative to the total weight of the reaction solvent.
  • the viscosity was 5,300 cP.
  • reaction temperature 60 °C / 6 hours after stirring for 25 °C, the solid content is to be maintained to 15% by weight relative to the total weight of the reaction solvent.
  • the viscosity was 5,500 cP.
  • reaction temperature 60 °C / 24 hours after stirring for 25 °C, the solid content is to be maintained to 15% by weight relative to the total weight of the reaction solvent.
  • the viscosity was 5,900 cP.
  • a polyimide film was prepared in the same manner as in Experimental Example 1, the physical properties were measured, and the results are shown in Table 4 below.
  • Comparative Example 7 is a case where the adhesive force is less than 0.2 (N / cm), the adhesive force is too weak, Comparative Example 8 is an adhesive force is too strong when the adhesive force is 2.3 (N / cm). Also, the laser peel energy is too high and may cause film damage during peeling. Such weak or strong adhesion will result in curls or product defects upon film peeling.
  • the polyamic acid resin prepared according to the present invention has an adhesive force of 0.2 to 2.0 N / cm, a peel energy of 200 mJ / cm 2 or less, and a thermal expansion coefficient of 10 ppm / ° C or less in a range of 100 to 350 ° C. It can be provided as a polyimide resin film.
  • the polyamic acid resin when the polyamic acid resin is prepared through the monomer split-input, the dosing time control and the optimization of the polymerization temperature according to the present invention, it has a low viscosity and excellent mechanical properties, heat resistance, and a low coefficient of thermal expansion. It can be widely used as an adhesive film on the glass substrate of the organic light emitting diode because it maintains the adhesive force and can be laser peeled at low energy so that it does not cause curl and product defects during peeling.

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PCT/KR2017/008493 2017-05-23 2017-08-07 레이저 박리 용이성 및 고내열성을 갖는 폴리아믹산 수지의 제조방법 및 이를 이용하여 제조한 폴리이미드 필름 WO2018216853A1 (ko)

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CN113166453B (zh) * 2018-11-30 2023-10-20 聚酰亚胺先端材料有限公司 由具有优异取向性能的聚酰亚胺膜制备的石墨片材及其制备方法
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