TWI739784B - Polyimideprecursor, method for producing thereof and method for producing polyimide film using the same - Google Patents
Polyimideprecursor, method for producing thereof and method for producing polyimide film using the same Download PDFInfo
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Abstract
Description
本申請案主張2015年12月31日向韓國智慧財產局提交之韓國專利申請號No.10-2015-0190977之優先權，本揭露之全部內容於此併入作為參考。 This application claims the priority of Korean Patent Application No. 10-2015-0190977 filed with the Korean Intellectual Property Office on December 31, 2015, and the entire content of this disclosure is hereby incorporated by reference.
本發明關於用於生產聚醯亞胺(polyimide)薄膜的聚醯亞胺前驅物組成物、用於製備其之方法、以及使用其生產聚醯亞胺薄膜之方法。 The present invention relates to a polyimide precursor composition for producing polyimide films, a method for preparing the same, and a method for producing polyimide films using the same.
聚醯亞胺材料具有優異的耐熱性與化學抗性，且因此係為非常適合用於可撓式顯示基板。 Polyimide materials have excellent heat resistance and chemical resistance, and therefore are very suitable for flexible display substrates.
在一般生產聚醯亞胺基板的方法中，聚醯胺酸(PAA)係藉由施用器或狹縫塗佈機的方式塗佈於載玻璃上，然後控制在高溫下進行熱醯亞胺化反應(thermal imidation reaction)，從而生產片狀基板。然而，該方法因為在對流式烘箱中以批次式方法而非連續式方法進行固化製程(即，熱醯亞胺化製程)而具有限制聚醯亞胺基板的生產的問題，而且由於400℃或以上的高製程溫度，故需要較長的製程時間。 In the general method of producing polyimide substrates, polyamide acid (PAA) is coated on the carrier glass by means of an applicator or slit coater, and then controlled at high temperature for thermal imidization Reaction (thermal imidation reaction), thereby producing a sheet-like substrate. However, this method has the problem of limiting the production of polyimide substrates due to the batch method rather than the continuous method in the convection oven for the curing process (that is, the thermal imidization process). Or above high process temperature, so longer process time is required.
為了增加在對流式烘箱中進行的固化製程的生產能力，將基板在120℃或以上的高溫下進行熱醯亞胺化，其中為了提高製程速度而沒有完全冷卻烘箱。在此情況中，由於使用的溶劑快速蒸發，因而降低基板薄膜的表面的平坦性(leveling characteristic)。出於這個理由，許多研究已經使用交聯劑(crosslinking agents)以解決此問題的(韓國專利號No.10-0889910)。 In order to increase the production capacity of the curing process in a convection oven, the substrate is thermally imidized at a high temperature of 120° C. or above, and the oven is not completely cooled in order to increase the process speed. In this case, since the solvent used evaporates quickly, the leveling characteristic of the surface of the substrate film is reduced. For this reason, many studies have used crosslinking agents to solve this problem (Korean Patent No. 10-0889910).
本發明為了解決發生在現有技術領域中的上述問題做了大量的努力，結果，發現使用具有特定含量的交聯劑的聚醯亞胺前驅物能提供即使在高溫進行醯亞胺化仍具有改善的表面特性的聚醯亞胺薄膜，從而完成本發明。 In order to solve the above-mentioned problems in the prior art, the present invention has made a lot of efforts. As a result, it was found that the use of a polyimide precursor with a specific content of crosslinking agent can provide improvements even at high temperatures. The surface characteristics of the polyimide film, thus completing the present invention.
在一態樣中，本發明提供用於製備聚醯亞胺前驅物之方法，其包含：添加並反應酸酐單體(anhydride monomer)與含有二胺(diamine)單體的聚合反應溶劑(polymerization solvent)，以獲得反應溶液；添加封端劑(end-capping agent)至反應溶液，然後使反應溶液反應，以合成聚醯胺酸；以及添加交聯劑至聚醯胺酸，然後混合。 In one aspect, the present invention provides a method for preparing a polyimide precursor, which comprises: adding and reacting an anhydride monomer and a polymerization solvent containing a diamine monomer. ) To obtain a reaction solution; adding an end-capping agent to the reaction solution, and then reacting the reaction solution to synthesize polyamide acid; and adding a cross-linking agent to polyamide acid, and then mixing.
在另一態樣中，本發明提供用於生產聚醯亞胺薄膜之方法，其包含：添加並反應酸酐單體與含有二胺單體的聚合反應溶劑，以獲得反應溶液；添加封端劑至反應溶液，然後使反應溶液反應，以合成聚醯胺酸；以及添加交聯劑至聚醯胺酸，然後混合，從而獲得聚醯亞胺前驅物；塗佈聚醯亞胺前驅物於基板上；以及將塗佈在基板上的聚醯亞胺前驅物在100℃或以上的溫度進行熱醯亞胺化。 In another aspect, the present invention provides a method for producing a polyimide film, which comprises: adding and reacting an acid anhydride monomer and a polymerization solvent containing a diamine monomer to obtain a reaction solution; adding a capping agent To the reaction solution, and then react the reaction solution to synthesize polyimide; and add a crosslinking agent to polyimide, and then mix to obtain a polyimide precursor; coating the polyimide precursor on the substrate And the polyimide precursor coated on the substrate is thermally imidized at a temperature of 100° C. or above.
第1圖係為根據本發明的範例的聚醯亞胺薄膜的影像。 Figure 1 is an image of a polyimide film according to an example of the present invention.
第2圖係為根據本發明的另一範例的聚醯亞胺薄膜的影像。 Figure 2 is an image of a polyimide film according to another example of the present invention.
第3圖係為根據本發明的又一範例的聚醯亞胺薄膜的影像。 Figure 3 is an image of a polyimide film according to another example of the present invention.
第4圖係為根據本發明的比較例的聚醯亞胺薄膜的影像。 Figure 4 is an image of a polyimide film according to a comparative example of the present invention.
第5圖係為根據本發明的另一比較例的聚醯亞胺薄膜的影像。 Figure 5 is an image of a polyimide film according to another comparative example of the present invention.
第6圖係為根據本發明的又一比較例的聚醯亞胺薄膜的影像。 Figure 6 is an image of a polyimide film according to another comparative example of the present invention.
第7圖係為根據本發明的再一比較例的聚醯亞胺薄膜的影像。 Figure 7 is an image of a polyimide film according to still another comparative example of the present invention.
在下文中，本發明的實施例與範例將參照附圖詳細地描述，以使所屬領域中具有通常知識者可以輕易地實行本發明。 Hereinafter, the embodiments and examples of the present invention will be described in detail with reference to the accompanying drawings, so that those with ordinary knowledge in the field can easily implement the present invention.
然而，本發明可以多種不同形式實施並且不限制於本文所描述的實施例與範例。於附圖中，將省略與敘述無關的部分，並且在整份說明書中使用相同的元件符號來表示相同的元件。 However, the present invention can be implemented in many different forms and is not limited to the embodiments and examples described herein. In the drawings, parts irrelevant to the description will be omitted, and the same reference numerals are used throughout the specification to denote the same elements.
在一態樣中，本發明提供製備聚醯亞胺前驅物之方法，其包含：添加並反應酸酐單體與含有二胺單體的聚合反應溶劑，以獲得反應溶液；添加封端劑至反應溶液，然後使反應溶液反應，以合成聚醯胺酸；以及添加交聯劑至聚醯胺酸，然後混合。 In one aspect, the present invention provides a method for preparing a polyimide precursor, which comprises: adding and reacting an acid anhydride monomer and a polymerization solvent containing a diamine monomer to obtain a reaction solution; adding a capping agent to the reaction Solution, and then react the reaction solution to synthesize polyamic acid; and add a crosslinking agent to polyamic acid, and then mix.
在本發明的一種實施例中，二胺單體可包含一種選擇自由苯二胺(phenylenediamine，PPDA)、4,4’-氧二苯胺(4,4'-oxydianiline，ODA)、4,4’-亞甲基二苯胺(4,4'-methylenedianiline，MDA)、間-甲苯胺(2,2'-二甲基-4,4'-二胺基苯甲 烷((m-tolidine)2,2'-dimethyl-4,4'-diaminobiphenyl))、1,3-雙(4'-胺基苯氧基)苯(1,3-bis(4'-aminophenoxyl)benzene，TPE-R)、2,2’-雙(三氯甲基)聯苯胺(2,2'-bis(trifluoromethyl)benzidine，TFMB)、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷(2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane，HFBAPP)、2,2-雙(3-胺基-4-羥基苯基)六氟丙烷(2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane，bis-AP-AF)、1,3-二胺基-2,4,5,6-四氟苯(1,3-diamino-2,4,5,6-tetrafluorobenzene，DRFB)、3,3'-二胺基二苯基碸(3,3'-diaminodiphenyl sulfone，DDS)、4,4'-二胺基二苯基硫醚(4,4'-diaminodiphenyl sulfide，ASD)、雙[4-(4-胺基苯氧基)苯基]碸(bis[4-(4-aminophenoxy)phenyl]sulfone，BAPS)、2,2-雙[4-(3-胺基苯氧基)苯基]碸(2,2-bis[4-(3-aminophenoxy)benzene]sulfone，m-BAPS)以及其組合所組成的群組的其一。較佳地，二胺單體可為PPDA。PPDA係為可顯示高耐熱性的芳族(aromatic)單體。 In an embodiment of the present invention, the diamine monomer may include a choice selected from phenylenediamine (PPDA), 4,4'-oxydianiline (ODA), 4,4' -Methylenedianiline (4,4'-methylenedianiline, MDA), m-toluidine (2,2'-dimethyl-4,4'-diaminobenzyl Alkyl ((m-tolidine)2,2'-dimethyl-4,4'-diaminobiphenyl)), 1,3-bis(4'-aminophenoxy)benzene (1,3-bis(4'-aminophenoxyl) )benzene, TPE-R), 2,2'-bis(trichloromethyl)benzidine (2,2'-bis(trifluoromethyl)benzidine, TFMB), 2,2-bis[4-(4-amino group) Phenoxy)phenyl]hexafluoropropane (2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, HFBAPP), 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoro Propane (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis-AP-AF), 1,3-diamino-2,4,5,6-tetrafluorobenzene (1,3-diamino -2,4,5,6-tetrafluorobenzene, DRFB), 3,3'-diaminodiphenyl sulfone (DDS), 4,4'-diaminodiphenyl sulfone Ether (4,4'-diaminodiphenyl sulfide, ASD), bis[4-(4-aminophenoxy)phenyl]sulfone (bis[4-(4-aminophenoxy)phenyl]sulfone, BAPS), 2,2 -Bis[4-(3-aminophenoxy)phenyl] sulfone (2,2-bis[4-(3-aminophenoxy)benzene]sulfone, m-BAPS) and other of the group consisting of its combination one. Preferably, the diamine monomer may be PPDA. PPDA is an aromatic monomer that can exhibit high heat resistance.
在本發明的一種實施例中，酸酐單體可為芳族二酸酐(aromatic dianhydride)單體。舉例而言，酸酐單體可包含選擇自由3,3’,4,4’-二苯甲酮四羧酸二酐(3,3',4,4'-benzophenonetetracarboxylicdianhydride，BTDA)、均苯四酸二酐(pyromellitic dianhydride，PMDA)、3,3’,4,4’-聯苯四羧酸二酐(3,3',4,4'-biphenyl tetracarboxylic acid dianhydride，BPDA)、2,2,-雙(3,4-脫水二羧基苯基)六氟丙烷二酐(2,2-bis(3,4-anhydrodicarboxyphenyl)-hexafluoropropane dianhydride，6FDA)、2,3,3’,4’-聯苯四羧酸二酐(2,3,3',4-biphenyl tetracarboxylic acid dianhydride，a-BPDA)、4,4’-氧雙鄰苯二甲酸酐(4,4'-oxydiphthalic anhydride，ODPA)、3,3’,4,4’-二苯基碸-四羧酸二酐 (3,3',4,4'-diphenylsulfone-tetracarboxylic dianhydride，DSDA)、2,2-雙[4-(3,4-二羧基苯氧基)苯基]丙烷二酐((2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride，BPADA)、氫醌二鄰苯二甲酸酐(hydroquinone diphthalic anhydride，HQDA)以及其組合所組成的群組之其一。可使用一或多種作為芳族二酸酐單體，舉例而言，可使用兩種或多種單體。 In an embodiment of the present invention, the acid anhydride monomer may be an aromatic dianhydride monomer. For example, the acid anhydride monomer may include 3,3',4,4'-benzophenonetetracarboxylic dianhydride (3,3',4,4'-benzophenonetetracarboxylicdianhydride, BTDA), pyromellitic acid Pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyl tetracarboxylic acid dianhydride (BPDA), 2,2,- Bis(3,4-anhydrodicarboxyphenyl)-hexafluoropropane dianhydride (2,2-bis(3,4-anhydrodicarboxyphenyl)-hexafluoropropane dianhydride, 6FDA), 2,3,3',4'-biphenyl Carboxylic dianhydride (2,3,3',4-biphenyl tetracarboxylic acid dianhydride, a-BPDA), 4,4'-oxydiphthalic anhydride (4,4'-oxydiphthalic anhydride, ODPA), 3, 3',4,4'-Diphenylsulfonium-tetracarboxylic dianhydride (3,3',4,4'-diphenylsulfone-tetracarboxylic dianhydride, DSDA), 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride ((2,2- One of the group consisting of bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, BPADA), hydroquinone diphthalic anhydride (HQDA), and combinations thereof. One or more can be used As the aromatic dianhydride monomer, for example, two or more monomers can be used.
在本發明的一種實施例中，聚合反應溶劑沒有特定限制，只要其係為使用在該領域的溶劑。舉例而言，聚合反應溶劑可包含選擇自由醯胺類(amide-based)溶劑、酮類(ketone-based)溶劑、醚類(ether-based)溶劑、酯類(ester-based)溶劑、對稱二醇二醚(symmetric glycol diether)溶劑、醚(ether)溶劑、以及其組合所組成的群組之其一。醯胺類溶劑可包含二甲基甲醯胺(dimethylformamide，DMF)、二甲基乙醯胺(dimethylacetamide，DMAC)、n-甲基吡咯烷酮(n-methylpyrrolidone，NMP)等，以及酮類溶劑可包含丙酮(acetion)、甲基乙基酮(methyl ethyl ketone，MEK)、甲基異丁基酮(methyl isobutyl ketone，MIBK)、環戊酮(cyclopentanone)、環己酮(cyclohexanone)等。醚類溶劑可包含四氫呋喃(tetrahydrofuran，THF)、1,3-二氧戊環(1,3-dioxolane)、與1,4-二噁烷(1,4-dioxane)，以及酯類溶劑可包含乙酸甲酯(methyl acetate)、乙酸乙酯(ethyl acetate)、乙酸丁酯(butyl acetate)、γ-丁內酯(γ-butyrolactone)、α-乙內酯(α-acetolactone)、β-丙內酯(β-propiolactone)、δ-戊內酯(δ-valerolactone)等。對稱二醇二醚溶劑可包含甲基單甘醇二甲醚(1,2-二甲氧基乙烷)(methyl monoglyme(1,2-dimethoxyethane))、甲基二甘醇二甲醚(雙(2-甲氧基乙基)醚)(methyl diglyme(bis(2-methoxyethyl)ether))、甲基三甘醇二甲醚(1,2-雙(2-甲氧 基乙氧基)乙烷)(methyl triglyme(1,2-bis(2-methoxyethoxy)ethane))、甲基四甘醇二甲醚(雙[2-(2-甲氧基乙氧基乙基)醚)(methyl tetraglyme(bis[2-(2-methoxyethoxyethyl)]ether))、乙基單甘醇二甲醚(1,2-二乙氧基乙烷)(ethyl monoglyme(1,2-diethoxyethane))、乙基二甘醇二甲醚(雙(2-乙氧基乙基)醚)(ethyl diglyme(bis(2-ethoxyethyl)ether))、丁基二甘醇二(雙(2-丁氧基乙基)醚)(butyl diglyme(bis(2-butoxyethyl)ether))等，以及醚溶劑可包含乙二醇二醚(glycol diether)、二丙二醇甲基醚(dipropylene glycol methyl ether)、三丙二醇甲基醚(tripropylene glycol methyl ether)、丙二醇正丙基醚(propylene glycol-n-propyl ether、二丙二醇正丙基醚(dipropylene glycol-n-propyl ether)、丙二醇正丁基醚(propylene glycol-n-butyl ether)、二丙二醇正丁基醚(dipropylene glycol-n-butyl ether)、三丙二醇正丙基醚(tripropylene glycol-n-propyl ether)、丙二醇苯基醚(propylene glycol phenyl ether)、二丙二醇甲基醚(dipropylene glycol methyl ether)、1,3-二氧戊環(1,3-dioxolane)、乙二醇單丁基醚(ethylene glycol monobutyl ether)、二甘醇單乙基醚(diethylene glycol monoethyl ether)、二甘醇單丁基醚(diethylene glycol monobutyl ether)、乙二醇單***(ethylene glycol monoethyl ether)等。在此聚合反應溶劑中，較佳地使用至少一溶劑。舉例而言，可使用NMP。 In an embodiment of the present invention, the polymerization reaction solvent is not particularly limited, as long as it is a solvent used in this field. For example, the polymerization solvent may include a choice of amide-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, and symmetrical two solvents. One of a group consisting of symmetric glycol diether solvents, ether solvents, and combinations thereof. The amide solvent may include dimethylformamide (DMF), dimethylacetamide (DMAC), n-methylpyrrolidone (NMP), etc., and the ketone solvent may include Acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclopentanone, cyclohexanone, etc. The ether solvent may include tetrahydrofuran (THF), 1,3-dioxolane (1,3-dioxolane), and 1,4-dioxane (1,4-dioxane), and the ester solvent may include Methyl acetate, ethyl acetate, butyl acetate, γ-butyrolactone, α-acetolactone, β-propiolactone Esters (β-propiolactone), δ-valerolactone (δ-valerolactone) and so on. The symmetrical glycol diether solvent may include methyl monoglyme (1,2-dimethoxyethane) (methyl monoglyme (1,2-dimethoxyethane)), methyl diglyme (two (2-methoxyethyl) ether) (methyl diglyme(bis(2-methoxyethyl)ether)), methyl triglyme (1,2-bis(2-methoxyethyl)ether) Ethoxy) ethane) (methyl triglyme (1,2-bis(2-methoxyethoxy)ethane)), methyl tetraglyme (bis[2-(2-methoxyethoxyethyl) )Ether)(methyl tetraglyme(bis[2-(2-methoxyethoxyethyl)]ether)), ethyl monoglyme(1,2-diethoxyethane)(ethyl monoglyme(1,2-diethoxyethane) )), ethyl diglyme (bis(2-ethoxyethyl)ether), ethyl diglyme (bis(2-ethoxyethyl)ether)), butyl diglyme(bis(2-ethoxyethyl)ether)), ethyl diglyme(bis(2-ethoxyethyl)ether)), butyl diglyme(bis(2-ethoxyethyl)ether) Oxyethyl) ether) (butyl diglyme (bis(2-butoxyethyl)ether)), etc., and the ether solvent may include glycol diether, dipropylene glycol methyl ether, three Tripropylene glycol methyl ether, propylene glycol-n-propyl ether, dipropylene glycol-n-propyl ether, propylene glycol-n-propyl ether n-butyl ether), dipropylene glycol-n-butyl ether, tripropylene glycol-n-propyl ether, propylene glycol phenyl ether, two Dipropylene glycol methyl ether, 1,3-dioxolane, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether glycol monoethyl ether), diethylene glycol monobutyl ether, ethylene glycol monoethyl ether, etc. In this polymerization solvent, at least one solvent is preferably used. For example , NMP can be used.
在本發明的實施例中，封端劑係為用於控制聚合反應，且可為酸酐型單體。舉例而言，酸酐型單體可選擇自由鄰苯二甲酸酐(phthalic anhydride，PA)、十四烷基琥珀酸酐(tetradecyl succinic anhydride，TSA)、十六烷基琥珀酸酐(hexadecyl succinic anhydride，HAS)、十八烷基琥珀酸酐(octadecyl succinic anhydride，OSA)以及其組合所組成的群組，且可較佳地為PA。封端劑可為能夠 控制聚合物(polymer)的分子量(molecular weight)、減少未反應材料的含量、並增加儲存穩定性的單酸酐(mono-anhydride)。 In the embodiment of the present invention, the end-capping agent is used to control the polymerization reaction, and may be an acid anhydride type monomer. For example, the acid anhydride monomer can be selected from phthalic anhydride (PA), tetradecyl succinic anhydride (TSA), and hexadecyl succinic anhydride (HAS). , Octadecyl succinic anhydride (OSA) and combinations thereof, and may preferably be PA. The blocking agent may be capable of Mono-anhydride that controls the molecular weight of the polymer, reduces the content of unreacted materials, and increases storage stability.
在本發明的一種實施例中，其方法可更包含，在合成聚醯胺酸後，為了控制固體含量與產物黏度到生產所需等級的添加溶劑的步驟。然而，添加的溶劑可為與聚合反應溶劑相同的溶劑。或者，不同於聚合反應溶劑的溶劑可用以增加產物的物理性質。 In an embodiment of the present invention, the method may further include the step of adding a solvent in order to control the solid content and the viscosity of the product after the polyamide acid is synthesized. However, the added solvent may be the same solvent as the polymerization reaction solvent. Alternatively, a solvent other than the polymerization solvent can be used to increase the physical properties of the product.
在本發明的一種實施例中，交聯劑可包含4,4’-亞甲基雙(N,N-雙環氧丙基苯胺(4,4’-methylenebis(N,N-diglycidylaniline))。較佳地，交聯劑可為具有下列結構式的4,4’-亞甲基雙(N,N-雙環氧丙基苯胺)(4,4’-methylenebis(N,N-diglycidylaniline))：
在本發明的實施例中，交聯劑之可添加量為基於使用的單體總重量的約2000至4000ppm。假若交聯劑之添加量少於2000ppm，所得聚醯亞胺薄膜的表面將為不良，且若交聯劑之添加量多於4000ppm，將降低聚醯亞胺薄膜的穿透度。 In the embodiment of the present invention, the crosslinking agent can be added in an amount of about 2000 to 4000 ppm based on the total weight of the monomers used. If the addition amount of the crosslinking agent is less than 2000 ppm, the surface of the obtained polyimide film will be poor, and if the addition amount of the crosslinking agent exceeds 4000 ppm, the penetration of the polyimide film will be reduced.
在另一態樣中，本發明提供用於聚醯亞胺薄膜之生產的聚醯亞胺薄膜前驅物，該聚醯亞胺薄膜藉由根據本發明生產聚醯亞胺薄膜之方法所生產， In another aspect, the present invention provides a polyimide film precursor for the production of a polyimide film, which is produced by the method for producing a polyimide film according to the present invention,
在本發明的實施例中，聚醯亞胺前驅物可包含聚醯胺酸聚合物。 In an embodiment of the present invention, the polyimide precursor may include a polyimide polymer.
在實施例中，藉由添加特定量的交聯劑於聚醯胺酸所製備的根據本發明的聚醯亞胺前驅物可提供即使在高溫進行醯亞胺化反應仍具有改善的表面特性的聚醯亞胺薄膜。具體地，可改善生產的聚醯亞胺薄膜的表面的平坦性，且可減少聚醯亞胺薄膜的穿透度的損耗。 In the embodiment, the polyimide precursor according to the present invention prepared by adding a specific amount of crosslinking agent to polyamide acid can provide a surface with improved surface characteristics even when the imidization reaction is carried out at high temperature. Polyimide film. Specifically, the flatness of the surface of the produced polyimide film can be improved, and the loss of the permeability of the polyimide film can be reduced.
在又一態樣中，本發明提供用以生產聚醯亞胺薄膜的方法，其包含：添加並反應酸酐單體與含有二胺單體的聚合反應溶劑，以獲得反應溶液；添加封端劑至反應溶液，然後使反應溶液反應以合成聚醯胺酸；添加交聯劑至聚醯胺酸，然後混合，從而獲得聚醯亞胺前驅物；塗佈聚醯亞胺前驅物於基板上；以及在基板上塗佈的聚醯亞胺在100℃或更高的溫度進行熱醯亞胺化。 In another aspect, the present invention provides a method for producing a polyimide film, which comprises: adding and reacting an acid anhydride monomer and a polymerization solvent containing a diamine monomer to obtain a reaction solution; adding a capping agent To the reaction solution, and then react the reaction solution to synthesize polyimide; add a crosslinking agent to the polyimide, and then mix to obtain a polyimide precursor; coating the polyimide precursor on the substrate; And the polyimide coated on the substrate is thermally imidized at a temperature of 100°C or higher.
在本發明的實施例中，熱醯胺化可於介於100℃至大約500℃之間、或介於大約100℃至大約400℃之間、或介於大約100℃至大約300℃之間、或介於大約100℃至大約200℃之間、或介於大約200℃至大約500℃之間、或介於大約300℃至大約500℃之間、或介於大約400℃至大約500℃之間的溫度進行，但不限於此。 In an embodiment of the present invention, the thermal amination may be between 100°C and about 500°C, or between about 100°C and about 400°C, or between about 100°C and about 300°C , Or between about 100°C to about 200°C, or between about 200°C to about 500°C, or between about 300°C to about 500°C, or between about 400°C to about 500°C The temperature between, but not limited to this.
在下文中，將藉由參照範例而更詳細地描述本發明，但這些範例不限制本發明的範疇。 Hereinafter, the present invention will be described in more detail by referring to examples, but these examples do not limit the scope of the present invention.
範例1 Example 1
在室溫下21.62g(0.2mol)完全溶解於529.2g的NMP，然後將52.96g(0.18mol)的BPDA與4.36g(0.02mol)的PMDA依序添加至溶液中。完全溶解後的1小時，添加0.43g(0.0029mol)的鄰苯二甲酸酐(PA)至溶液中，然後使其反應16小時，從而獲得聚醯胺酸(PAA)聚合物。之後，將0.15874g(對應於基於單體 (PPDA、BPDA、與PMDA)的總重量為2000ppm)的4,4’-亞甲基雙(N,N-雙環氧丙基苯胺)溶解在NMP(與用於反應中的溶劑相同)中，然後添加並與PAA聚合物混合。 21.62g (0.2mol) was completely dissolved in 529.2g of NMP at room temperature, and then 52.96g (0.18mol) of BPDA and 4.36g (0.02mol) of PMDA were sequentially added to the solution. One hour after the complete dissolution, 0.43 g (0.0029 mol) of phthalic anhydride (PA) was added to the solution, and then allowed to react for 16 hours to obtain a polyamide acid (PAA) polymer. After that, 0.15874g (corresponding to the monomer-based (The total weight of PPDA, BPDA, and PMDA is 2000ppm) 4,4'-methylenebis(N,N-bisepoxypropylaniline) is dissolved in NMP (the same solvent used in the reaction) , And then add and mix with PAA polymer.
範例2 Example 2
在室溫下21.62g(0.2mol)完全溶解於529.2g的NMP，然後52.96g(0.18mol)的BPDA與4.36g(0.02mol)的PMDA依序添加至溶液中。完全溶解後的1小時，添加0.43g(0.0029mol)的鄰苯二甲酸酐(PA)至溶液中，然後使其反應16小時，從而獲得聚醯胺酸(PAA)聚合物。之後，0.23811g(對應於基於單體(PPDA、BPDA、與PMDA)的總重量為3000ppm)的4,4’-亞甲基雙(N,N-雙環氧丙基苯胺)溶解在NMP(與用於反應中的溶劑相同)中，然後添加並與PAA聚合物混合。 21.62g (0.2mol) was completely dissolved in 529.2g of NMP at room temperature, and then 52.96g (0.18mol) of BPDA and 4.36g (0.02mol) of PMDA were sequentially added to the solution. One hour after the complete dissolution, 0.43 g (0.0029 mol) of phthalic anhydride (PA) was added to the solution, and then allowed to react for 16 hours to obtain a polyamide acid (PAA) polymer. After that, 0.23811g (corresponding to 3000ppm based on the total weight of monomers (PPDA, BPDA, and PMDA)) of 4,4'-methylenebis(N,N-diglycidaniline) was dissolved in NMP( It is the same as the solvent used in the reaction), and then added and mixed with the PAA polymer.
範例3 Example 3
在室溫下21.62g(0.2mol)完全溶解於529.2g的NMP，然後52.96g(0.18mol)的BPDA與4.36g(0.02mol)的PMDA依序添加至溶液中。完全溶解後的1小時，添加0.43g(0.0029mol)的鄰苯二甲酸酐(PA)至溶液中，然後使其反應16小時，從而獲得聚醯胺酸(PAA)聚合物。之後，0.31748g(對應於基於單體(PPDA、BPDA、與PMDA)的總重量為4000ppm)的4,4’-亞甲基雙(N,N-雙環氧丙基苯胺)溶解在溶劑中，然後添加並與PAA聚合物混合。 21.62g (0.2mol) was completely dissolved in 529.2g of NMP at room temperature, and then 52.96g (0.18mol) of BPDA and 4.36g (0.02mol) of PMDA were sequentially added to the solution. One hour after the complete dissolution, 0.43 g (0.0029 mol) of phthalic anhydride (PA) was added to the solution, and then allowed to react for 16 hours to obtain a polyamide acid (PAA) polymer. Afterwards, 0.31748g (corresponding to 4000ppm based on the total weight of monomers (PPDA, BPDA, and PMDA)) of 4,4'-methylenebis(N,N-bisglycidylaniline) was dissolved in the solvent , And then add and mix with PAA polymer.
比較例1 Comparative example 1
在室溫下21.62g(0.2mol)完全溶解於529.2g的NMP，然後52.96g(0.18mol)的BPDA與4.36g(0.02mol)的PMDA依序添加至溶液中。完全溶解後的1小時，添加0.43g(0.0029mol)的鄰苯二甲酸酐(PA)至溶液中，然後使其反應 16小時，從而獲得聚醯胺酸(PAA)聚合物。之後，NMP(與用於範例1中的溶劑相同)被添加並與PAA聚合物混合。 21.62g (0.2mol) was completely dissolved in 529.2g of NMP at room temperature, and then 52.96g (0.18mol) of BPDA and 4.36g (0.02mol) of PMDA were sequentially added to the solution. 1 hour after complete dissolution, add 0.43g (0.0029mol) of phthalic anhydride (PA) to the solution, and then make it react For 16 hours, a polyamide acid (PAA) polymer was obtained. After that, NMP (the same solvent used in Example 1) was added and mixed with the PAA polymer.
比較例2 Comparative example 2
在室溫下21.62g(0.2mol)完全溶解於529.2g的NMP，然後52.96g(0.18mol)的BPDA與4.36g(0.02mol)的PMDA依序添加至溶液中。完全溶解後的1小時，添加0.43g(0.0029mol)的鄰苯二甲酸酐(PA)至溶液中，然後使其反應16小時，從而獲得聚醯胺酸(PAA)聚合物。之後，0.07937g(對應於基於單體(PPDA、BPDA、與PMDA)的總重量為1000ppm)的4,4’-亞甲基雙(N,N-雙環氧丙基苯胺)溶解在NMP(與用於反應中的溶劑相同)中，然後添加並與PAA聚合物混合。 21.62g (0.2mol) was completely dissolved in 529.2g of NMP at room temperature, and then 52.96g (0.18mol) of BPDA and 4.36g (0.02mol) of PMDA were sequentially added to the solution. One hour after the complete dissolution, 0.43 g (0.0029 mol) of phthalic anhydride (PA) was added to the solution, and then allowed to react for 16 hours to obtain a polyamide acid (PAA) polymer. After that, 0.07937g (corresponding to 1000 ppm based on the total weight of the monomers (PPDA, BPDA, and PMDA)) of 4,4'-methylenebis(N,N-diglycidaniline) was dissolved in NMP( It is the same as the solvent used in the reaction), and then added and mixed with the PAA polymer.
比較例3 Comparative example 3
在室溫下21.62g(0.2mol)完全溶解於529.2g的NMP，然後52.96g(0.18mol)的BPDA與4.36g(0.02mol)的PMDA依序添加至溶液中。完全溶解後的1小時，添加0.43g(0.0029mol)的鄰苯二甲酸酐(PA)至溶液中，然後使其反應16小時，從而獲得聚醯胺酸(PAA)聚合物。之後，0.119055g(對應於基於單體(PPDA、BPDA、與PMDA)的總重量為1500ppm)的4,4’-亞甲基雙(N,N-雙環氧丙基苯胺)溶解在NMP(與用於反應中的溶劑相同)中，然後添加並與PAA聚合物混合。 21.62g (0.2mol) was completely dissolved in 529.2g of NMP at room temperature, and then 52.96g (0.18mol) of BPDA and 4.36g (0.02mol) of PMDA were sequentially added to the solution. One hour after the complete dissolution, 0.43 g (0.0029 mol) of phthalic anhydride (PA) was added to the solution, and then allowed to react for 16 hours to obtain a polyamide acid (PAA) polymer. After that, 0.119055g (corresponding to 1500ppm based on the total weight of monomers (PPDA, BPDA, and PMDA)) of 4,4'-methylenebis(N,N-diglycidaniline) was dissolved in NMP( It is the same as the solvent used in the reaction), and then added and mixed with the PAA polymer.
比較例4 Comparative example 4
在室溫下21.62g(0.2mol)完全溶解於529.2g的NMP，然後52.96g(0.18mol)的BPDA與4.36g(0.02mol)的PMDA依序添加至溶液中。完全溶解後的1小時，添加0.43g(0.0029mol)的鄰苯二甲酸酐(PA)至溶液中，然後使其反應 16小時，從而獲得聚醯胺酸(PAA)聚合物。之後，0.39685g(對應於基於單體(PPDA、BPDA、與PMDA)的總重量為5000ppm)的4,4’-亞甲基雙(N,N-雙環氧丙基苯胺)溶解在NMP(與用於反應中的溶劑相同)中，然後添加並與PAA聚合物混合。 21.62g (0.2mol) was completely dissolved in 529.2g of NMP at room temperature, and then 52.96g (0.18mol) of BPDA and 4.36g (0.02mol) of PMDA were sequentially added to the solution. 1 hour after complete dissolution, add 0.43g (0.0029mol) of phthalic anhydride (PA) to the solution, and then make it react For 16 hours, a polyamide acid (PAA) polymer was obtained. After that, 0.39685g (corresponding to 5000ppm based on the total weight of monomers (PPDA, BPDA, and PMDA)) of 4,4'-methylenebis(N,N-diglycidaniline) was dissolved in NMP( It is the same as the solvent used in the reaction), and then added and mixed with the PAA polymer.
測試範例1 Test example 1
藉由貝克施用器(Baker applicator，YBA-4)將於範例1至3與比較例1至4製備的每一個聚醯亞胺前驅物於基板(液晶顯示器玻璃，LCD Glass SM TECH，新玻璃(new glass)(200mm x 200mm x 0.63mm)上塗佈成400μm的濕性厚度，然後控制在120℃的對流式烘箱中進行熱醯亞胺化反應。此後，將每一個基板於速率3℃/min加熱，在450℃維持1小時，然後緩慢地冷卻。冷卻之後，回收基板薄膜，並分析薄膜的外觀與光學性質。分析的結果顯示在第1圖至第4圖與表1及表2。 Each polyimide precursor prepared in Examples 1 to 3 and Comparative Examples 1 to 4 was applied to the substrate (liquid crystal display glass, LCD Glass SM TECH, new glass ( New glass) (200mm x 200mm x 0.63mm) was coated to a wet thickness of 400μm, and then controlled to conduct thermal imidization reaction in a convection oven at 120°C. Thereafter, each substrate was heated at a rate of 3°C/ Min heating, maintaining at 450°C for 1 hour, and then slowly cooling. After cooling, the substrate film was recovered, and the appearance and optical properties of the film were analyzed. The results of the analysis are shown in Figures 1 to 4 and Tables 1 and 2.
如第1圖至第7圖所示，當4,4’-亞甲基雙(N,N-雙環氧丙基苯胺)添加的量為2000ppm、3000ppm、與4000ppm(第1圖至第3圖)，薄膜表面的平坦性係為良好，而當未添加4,4’-亞甲基雙(N,N-雙環氧丙基苯胺)(第4圖)與添加量為1000ppm、1500ppm與5000ppm(第5圖至第7圖)時，薄膜表面的平坦性係為不良。 As shown in Figures 1 to 7, when 4,4'-methylenebis(N,N-diglycidylaniline) is added in amounts of 2000ppm, 3000ppm, and 4000ppm (Figures 1 to 3 Figure), the flatness of the film surface is good, and when 4,4'-methylenebis(N,N-bisglycidylaniline) is not added (Figure 4) and the addition amount is 1000ppm, 1500ppm and At 5000 ppm (Figures 5 to 7), the flatness of the film surface is poor.
此外，如上列的表1與表2所示，當4,4’-亞甲基雙(N,N-雙環氧丙基苯胺)的添加量低於2000ppm或不低於5000ppm時，薄膜的穿透度快速地減少。 In addition, as shown in Table 1 and Table 2 above, when the addition amount of 4,4'-methylenebis(N,N-diglycidylaniline) is less than 2000ppm or not less than 5000ppm, the film’s The penetration decreases rapidly.
如上文所描述，藉由添加特定量的交聯劑至聚醯胺酸所製備的根據本發明的聚醯亞胺前驅物可以提供即使在高溫進行醯亞胺化時仍具有改善的表面特性的聚醯亞胺薄膜。具體地，可改善生產的聚醯亞胺薄膜的表面的平坦性，且可減少聚醯亞胺薄膜的穿透度的損耗。 As described above, the polyimide precursor according to the present invention prepared by adding a specific amount of a crosslinking agent to polyamide acid can provide improved surface properties even when the imidization is carried out at high temperature. Polyimide film. Specifically, the flatness of the surface of the produced polyimide film can be improved, and the loss of the permeability of the polyimide film can be reduced.
本發明的上述實施例係僅供說明之目的，且所屬技術領域中具有通常知識者將了解的是，可在不改變本發明的技術精神與基本特徵下，可對其進行形式與細節的各種改變。因此，實施例僅供說明意義上理解且不以限制所有態樣為目的。舉例而言，以單一形式描述的每一個成分可以分散方式執行，且同樣地，以分散方式所述的成分可以組合的方式執行。 The above-mentioned embodiments of the present invention are for illustrative purposes only, and those with ordinary knowledge in the technical field will understand that various forms and details can be carried out without changing the technical spirit and basic features of the present invention. Change. Therefore, the embodiments are only understood in an illustrative sense and are not intended to limit all aspects. For example, each component described in a single form may be executed in a decentralized manner, and likewise, the components described in a decentralized manner may be executed in a combined manner.
當藉由參照各種本發明中實施例描述本發明，所屬技術領域中具有通常知識者應了解的是，在不脫離如所附申請專利範圍及其等效物定義的本揭露之精神與範疇，可對其進行形式或細節上的各種改變。 When the present invention is described by referring to various embodiments of the present invention, those skilled in the art should understand that, without departing from the spirit and scope of the present disclosure as defined by the appended patent scope and its equivalents, Various changes in form or details can be made to it.
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| KR101959807B1 (en) * | 2018-08-22 | 2019-03-20 | 에스케이씨코오롱피아이 주식회사 | Polyimide Varnish for Coating Conductor Comprising Aromatic Carboxylic Acid and Method for Preparing the Same |
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