TWI837970B - Polyamic acid composition and polyimide film prepared with the same - Google Patents
Polyamic acid composition and polyimide film prepared with the same Download PDFInfo
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- TWI837970B TWI837970B TW111145361A TW111145361A TWI837970B TW I837970 B TWI837970 B TW I837970B TW 111145361 A TW111145361 A TW 111145361A TW 111145361 A TW111145361 A TW 111145361A TW I837970 B TWI837970 B TW I837970B
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- polyamine
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- polyamide
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- 239000000203 mixture Substances 0.000 title claims abstract description 72
- 229920001721 polyimide Polymers 0.000 title claims abstract description 56
- 229920005575 poly(amic acid) Polymers 0.000 title abstract description 23
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000000126 substance Substances 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 239000004593 Epoxy Substances 0.000 claims abstract description 28
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000004985 diamines Chemical class 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 229920000768 polyamine Polymers 0.000 claims description 37
- 239000004952 Polyamide Substances 0.000 claims description 27
- 229920002647 polyamide Polymers 0.000 claims description 27
- -1 imidazole compound Chemical class 0.000 claims description 21
- 238000004383 yellowing Methods 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 10
- FAUAZXVRLVIARB-UHFFFAOYSA-N 4-[[4-[bis(oxiran-2-ylmethyl)amino]phenyl]methyl]-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC(CC=2C=CC(=CC=2)N(CC2OC2)CC2OC2)=CC=1)CC1CO1 FAUAZXVRLVIARB-UHFFFAOYSA-N 0.000 claims description 10
- 230000009477 glass transition Effects 0.000 claims description 9
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- LBVMWHCOFMFPEG-UHFFFAOYSA-N 3-methoxy-n,n-dimethylpropanamide Chemical compound COCCC(=O)N(C)C LBVMWHCOFMFPEG-UHFFFAOYSA-N 0.000 claims description 4
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 4
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 claims description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ABMDIECEEGFXNC-UHFFFAOYSA-N n-ethylpropanamide Chemical compound CCNC(=O)CC ABMDIECEEGFXNC-UHFFFAOYSA-N 0.000 claims description 2
- XIPFMBOWZXULIA-UHFFFAOYSA-N pivalamide Chemical compound CC(C)(C)C(N)=O XIPFMBOWZXULIA-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 claims 1
- 229940018564 m-phenylenediamine Drugs 0.000 claims 1
- 239000004642 Polyimide Substances 0.000 abstract description 31
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 13
- OVASAEXSPYGGES-UHFFFAOYSA-N C1C2C(C(OC3=O)=O)C3C1CC2(C1=O)CCC21CC1CC2C2C(=O)OC(=O)C12 Chemical compound C1C2C(C(OC3=O)=O)C3C1CC2(C1=O)CCC21CC1CC2C2C(=O)OC(=O)C12 OVASAEXSPYGGES-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 2
- XPAQFJJCWGSXGJ-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(N)C=C1 XPAQFJJCWGSXGJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- RPOHXHHHVSGUMN-UHFFFAOYSA-N 1-n,4-n-bis(4-aminophenyl)benzene-1,4-dicarboxamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(C(=O)NC=2C=CC(N)=CC=2)C=C1 RPOHXHHHVSGUMN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
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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
- C08G73/14—Polyamide-imides
-
- 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
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
-
- 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
- C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
-
- 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
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
-
- 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
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
- G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
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- Manufacturing & Machinery (AREA)
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- Theoretical Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
本揭露是關於一種聚醯胺酸組合物以及用其製備的聚醯亞胺薄膜。具體來說,本揭露是關於用於製造顯示器基板的聚醯胺酸組合物以及作為聚醯胺酸之固化產物的聚醯亞胺薄膜。The present disclosure relates to a polyamic acid composition and a polyimide film prepared therefrom. Specifically, the present disclosure relates to a polyamic acid composition used for manufacturing a display substrate and a polyimide film as a cured product of polyamic acid.
各種類型和尺寸的顯示器,從如手機的小型顯示器到液晶顯示器或電漿電視或戶外告示牌(公共訊息顯示器(public information displays, PIDS)以及數字訊息顯示器(digital information displays, DIDs))。特別是隨著社會發展到普及的時代,亦即先進的知識、資訊社會,對具有簡單性以及移動性之便攜式裝置的需求正在蓬勃發展。相對地,更薄、更輕、更便於攜帶、以及可以像紙一樣折疊和像卷軸一樣捲曲之可撓式顯示器的技術正在興起,且正在成為新的成長引擎業務。Displays of various types and sizes, from small displays such as mobile phones to LCD or plasma TVs or outdoor billboards (public information displays (PIDS) and digital information displays (DIDs)). In particular, as society develops into the era of popularization, that is, the advanced knowledge and information society, the demand for portable devices with simplicity and mobility is booming. In contrast, the technology of flexible displays that are thinner, lighter, easier to carry, and can be folded like paper and rolled up like a scroll is emerging and is becoming a new growth engine business.
在這樣的環境下,藉由固化和亞胺化聚醯胺酸(藉由聚合二酐單體和二胺單體所製備)製備的聚醯亞胺薄膜具有優異的耐熱性、耐化學性、機械強度、電性、以及尺寸穩定度等,因此被廣泛利用於電性/電子裝置領域、半導體領域等。特別是人們越來越關注將薄膜作為可撓性顯示器的基板材料。In such an environment, polyimide films prepared by curing and imidizing polyamide (prepared by polymerizing dianhydride monomers and diamine monomers) have excellent heat resistance, chemical resistance, mechanical strength, electrical properties, and dimensional stability, and are therefore widely used in the fields of electrical/electronic devices, semiconductors, etc. In particular, people are paying more and more attention to using films as substrate materials for flexible displays.
然而,為了將薄膜用於顯示應用產品,需具有高透明度、高機械強度、光學性能、黃化指數和機械性能,同時不存在因折疊引發的捲曲或裂紋這類的微缺陷。However, in order to use the film for display applications, it needs to have high transparency, high mechanical strength, optical properties, yellowing index and mechanical properties, while being free of micro defects such as curling or cracks caused by folding.
因此,需要開發具有低黃化指數的聚醯亞胺,其適合應用於可撓性基板,且保持優異的熱性能如耐熱性,同時具有優異的強度和伸長率。Therefore, there is a need to develop polyimide with a low yellowing index that is suitable for application in flexible substrates and maintains excellent thermal properties such as heat resistance while having excellent strength and elongation.
[技術課題] 本揭露之目的是提供一種具有優異伸長率和強度,且同時維持低黃化指數和優異熱性能的聚醯胺酸化合物,以及用其製備的聚醯亞胺薄膜。 [Technical topic] The purpose of this disclosure is to provide a polyamide compound having excellent elongation and strength while maintaining a low yellowing index and excellent thermal properties, and a polyimide film prepared therefrom.
此外,本揭露另一個目的在於提供一種以上述聚醯亞胺薄膜作為基板的可撓性顯示裝置。In addition, another object of the present disclosure is to provide a flexible display device using the polyimide film as a substrate.
[技術手段] 本揭露可具有各種變化且可具有多個實施例,因此如附圖所示並將詳細描述具體實施例。然而,這些描述不旨在將本揭露限於具體實施例,而應理解為包括所有包含在本揭露之精神和範圍內的修改、等效物和替代物。 [Technical means] The present disclosure may have various variations and may have multiple embodiments, so specific embodiments will be described in detail as shown in the accompanying drawings. However, these descriptions are not intended to limit the present disclosure to specific embodiments, but should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present disclosure.
本案中所使用的用語僅用於描述具體實施例,並不旨在限制本揭露。除非上下文另有明確說明,單數表達包括複數表達。在本案中,諸如「包括」、「具有」等用語旨在表示存在於說明書中描述的特徵、數量、步驟、操作、成分及前述之組合。應理解的是,這些術語不預先排除存在或添加一個或多個其他特徵或數量、步驟、操作、組件、部件或其組合的可能性。The terms used in this case are only used to describe specific embodiments and are not intended to limit the present disclosure. Unless the context clearly indicates otherwise, singular expressions include plural expressions. In this case, terms such as "including", "having", etc. are intended to indicate the presence of the features, quantities, steps, operations, components, and combinations thereof described in the specification. It should be understood that these terms do not preemptively exclude the possibility of the presence or addition of one or more other features or quantities, steps, operations, components, parts, or combinations thereof.
當藉由列舉範圍、優選範圍或優選上限值、和優選下限值所給出的數量、濃度或其他數值或參數時,應理解,從任何範圍上限或優選數值以及任何範圍下限或優選數值中的任何一對所形成的所有範圍都被具體揭露,無論範圍是否個別地揭露。When an amount, concentration or other value or parameter is given by listing a range, a preferred range or a preferred upper limit, and a preferred lower limit, it should be understood that all ranges formed from any pair of any range upper limit or preferred value and any range lower limit or preferred value are specifically disclosed, regardless of whether the range is disclosed individually.
當本文中說明數值範圍時,除非另有說明,否則其範圍不限於端點,且在該範圍內之本揭露的範圍不限於在定義範圍時列舉的特定值。When numerical ranges are described herein, unless otherwise stated, the ranges are not limited to the endpoints, and the scope of the present disclosure within the range is not limited to the specific values recited when defining the range.
除非另有定義,否則本文使用的所有用語,包括技術或科學用語,具有本揭露所屬技術領域中具有通常知識者所共同理解的相同含意。諸如在常用詞典中定義的用語,應理解為具有與相關技術脈絡中的含義一致的含義,且不應被解釋為理想或過於形式化的含義,除非在本案中有明確定義。以下將描述實現本揭露的具體細節。Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meanings as commonly understood by persons of ordinary skill in the art to which the present disclosure belongs. Terms defined in commonly used dictionaries should be understood to have meanings consistent with those in the relevant technical context and should not be interpreted as ideal or overly formalized meanings unless clearly defined in the present case. The following will describe specific details for implementing the present disclosure.
本揭露是關於一種聚醯胺酸組合物。The present disclosure relates to a polyamino acid composition.
在本揭露的一個總體面向,聚醯胺酸組合物可包括:聚醯胺酸,包括,作為聚合單元,選自下列至少一種:由化學式1所示的二酐單體以及由化學式2或化學式3所示的二胺單體中: [化學式1] [化學式2] [化學式3] 咪唑基(imidazole-based)化合物;環氧基(epoxy-based)化合物;以及有機溶劑。 In one general aspect of the present disclosure, the polyamine composition may include: polyamine, including, as a polymerizable unit, at least one selected from the following: a dianhydride monomer represented by Chemical Formula 1 and a diamine monomer represented by Chemical Formula 2 or Chemical Formula 3: [Chemical Formula 1] [Chemical formula 2] [Chemical formula 3] Imidazole-based compounds; epoxy-based compounds; and organic solvents.
根據本揭露製備的聚醯胺酸組合物,其具有聚醯亞胺獨有之優異的熱性能,同時具有低黃化指數,並且還具有優異的機械性能,例如強度和伸長率。因此,聚醯胺酸組合物適合作為顯示器用材料,作為聚醯胺酸組合物之固化物的聚醯亞胺薄膜作為顯示器基板用材料是有益的。The polyamic acid composition prepared according to the present disclosure has excellent thermal properties unique to polyimide, a low yellowing index, and excellent mechanical properties such as strength and elongation. Therefore, the polyamic acid composition is suitable as a display material, and the polyimide film as a cured product of the polyamic acid composition is beneficial as a display substrate material.
在本揭露中,由化學式1所示的化合物稱為降冰片烷-2-螺-α-環戊酮-α′-螺-2″-降冰片烷-5,5″,6,6″-四羧酸二酐(norbornane-2-spiro-α-cyclopentanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic acid dianhydride, CpODA),CpODA可以是立體異構物的混合物或可以是一種特定的立體異構。立體異構物沒有特別限制,但優選的立體異構物可包括反-內-內-降冰片烷-2-螺-α-環戊酮-α′-螺-2″-降冰片烷-5,5″,6,6″-四羧酸二酐(trans-endo-endo-norbornane-2-spiro-α-cyclopentanone-α′-spiro-2″-norbornane-5,5″,6,6"-tetracarboxylic dianhydride, CpODA-tee)和順-內-內-降冰片烷-2-螺-α-環戊酮-α′-螺-2″-降冰片烷-5,5″,6,6″-四羧酸二酐(cis-endo-endo-norbornane-2-spiro-α-cyclopentanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride, CpODA-cee)。 (CpODA) (CpODA-tee) (CpODA-cee) In the present disclosure, the compound represented by Chemical Formula 1 is referred to as norbornane-2-spiro-α-cyclopentanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic acid dianhydride (CpODA). CpODA may be a mixture of stereoisomers or may be a specific stereoisomer. The stereoisomers are not particularly limited, but preferred stereoisomers may include trans-endo-endo-norbornane-2-spiro-α-cyclopentanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride (CpODA-tee) and cis-endo-endo-norbornane-2-spiro-α-cyclopentanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride (CpODA-tee). CpODA-cee). (CpODA) (CpODA-tee) (CpODA-cee)
在一個實施例中,至少50莫耳%或更多,甚至更優選地,63莫耳%或更多的CpODA可以是CpODA-tee。在另一個例示中,至少30莫耳%或更多,甚至更優選地,至少37莫耳%或更多的CpODA可以是CpODA-cee。在另一個例示中,CpODA中CpODA-tee和CpODA-cee之總量可以至少為80莫耳%或更多,甚至更優選地,83莫耳%或更多,但含量範圍不限於此。In one embodiment, at least 50 mol% or more, even more preferably, 63 mol% or more of CpODA may be CpODA-tee. In another exemplification, at least 30 mol% or more, even more preferably, at least 37 mol% or more of CpODA may be CpODA-cee. In another exemplification, the total amount of CpODA-tee and CpODA-cee in CpODA may be at least 80 mol% or more, even more preferably, 83 mol% or more, but the content range is not limited thereto.
在本揭露中,由化學式2所示的化合物稱為4,4'-二氨基苯甲醯苯胺(4,4'-diaminobenzanilide, DABAN),此外,由化學式3所示的化合物稱為N,N'-雙(4-氨基苯基)苯-1,4-二甲醯胺(N,N'-bis(4-aminophenyl)benzene-1,4-dicarboxamide, DATA)。In the present disclosure, the compound represented by Chemical Formula 2 is referred to as 4,4'-diaminobenzanilide (DABAN), and the compound represented by Chemical Formula 3 is referred to as N,N'-bis(4-aminophenyl)benzene-1,4-dicarboxamide (DATA).
在本揭露中,聚醯胺酸組合物還可包括由化學式4所示的二酐單體,且可以具有伴隨二酐單體的聚合單元: [化學式4] In the present disclosure, the polyamine composition may further include a dianhydride monomer as shown in Chemical Formula 4, and may have a polymerized unit associated with the dianhydride monomer: [Chemical Formula 4]
由化學式4所示的化合物稱為(4arH,8acH)-十氫-1t,4t:5c,8c-二甲萘-2c,3c,6c,7c-四羧酸二酐((4arH,8acH)-decahydro-1t,4t:5c,8c-dimethanonaphthalene-2c,3c,6c,7c-tetracarboxylic dianhydride, DNDAxx)。The compound represented by Chemical Formula 4 is called (4arH,8acH)-decahydro-1t,4t:5c,8c-dimethanonaphthalene-2c,3c,6c,7c-tetracarboxylic dianhydride (DNDAxx).
在本揭露中,由化學式4所示的二酐單體可包含總二酐單體成分比例的20莫耳%或更少、優選地15莫耳%或更少、13莫耳%或更少、10莫耳%或更少、8莫耳%或更少的、7莫耳%或更少,5莫耳%或更少、3莫耳%或更少、或2莫耳%或更少、或0莫耳%。In the present disclosure, the dianhydride monomer represented by Chemical Formula 4 may comprise 20 mol % or less, preferably 15 mol % or less, 13 mol % or less, 10 mol % or less, 8 mol % or less, 7 mol % or less, 5 mol % or less, 3 mol % or less, or 2 mol % or less, or 0 mol % of the total dianhydride monomer component ratio.
在本揭露中,由化學式2所示的二胺單體可包含總二胺單體成分比例的70莫耳%或更多,所述比例的下限可以是,例如75莫耳%、78莫耳%、80莫耳%、82莫耳%、85莫耳%、87莫耳%、90莫耳%、92莫耳%、94莫耳%、95莫耳% 、97莫耳%、99莫耳%、或100莫耳%或更多,而其比例的上限可以是,例如100莫耳%、99莫耳%、98莫耳%、97莫耳%、96莫耳%、95莫耳%、94莫耳%、93莫耳%、92莫耳%、91莫耳%、90莫耳%、或88莫耳%或更少。In the present disclosure, the diamine monomer represented by Chemical Formula 2 may comprise 70 mol% or more of the total diamine monomer component ratio, the lower limit of the ratio may be, for example, 75 mol%, 78 mol%, 80 mol%, 82 mol%, 85 mol%, 87 mol%, 90 mol%, 92 mol%, 94 mol%, 95 mol%, 97 mol%, 99 mol%, or 100 mol% or more, and the upper limit of the ratio may be, for example, 100 mol%, 99 mol%, 98 mol%, 97 mol%, 96 mol%, 95 mol%, 94 mol%, 93 mol%, 92 mol%, 91 mol%, 90 mol%, or 88 mol% or less.
在本揭露中,藉由使用適合於聚醯胺酸的咪唑基(imidazole-based)化合物,可以製備出具有優異機械性能,如透明性、伸長率和脆性(強度)等的聚醯亞胺。In the present disclosure, by using an imidazole-based compound suitable for polyimide, polyimide with excellent mechanical properties such as transparency, elongation and brittleness (strength) can be prepared.
在本揭露中,咪唑基化合物可包括2-苯基咪唑、苯并咪唑、1,2-二甲基咪唑、1-甲基咪唑、2-甲基咪唑、以及咪唑等其中一種或前述之組合。優選地咪唑基化合物可為2-苯基咪唑或苯并咪唑,更優選地可為2-苯基咪唑。In the present disclosure, the imidazole compound may include 2-phenylimidazole, benzimidazole, 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, and imidazole, or a combination thereof. Preferably, the imidazole compound may be 2-phenylimidazole or benzimidazole, and more preferably, 2-phenylimidazole.
此外,在本揭露中,以1莫耳聚醯胺酸之重複單元為基準,咪唑基化合物的含量可為0.1至40莫耳%。該比例的下限可以是,例如0.5莫耳%、1.0莫耳%、1.5莫耳%、2莫耳%、2.5莫耳%、3莫耳%、3.5莫耳%、4.0莫耳%、4.5莫耳%、4.7mol %、4.9 莫耳%、5.0 莫耳%、5.2 莫耳%、5.5 莫耳%、6.0 莫耳%、6.5 莫耳%、7.0 莫耳%、7.5 莫耳%、8.0 莫耳%、8.5 莫耳%、9.0 莫耳%、9.5 莫耳%、或10莫耳%或更多,而其比例的上限可以是,例如35莫耳%、30莫耳%、28莫耳%、26莫耳%、24莫耳%、22莫耳%、20莫耳%、18莫耳%、15莫耳%、12莫耳%、或10莫耳%或更少。當咪唑基化合物的含量過少時,例如:當咪唑基化合物的含量小於0.1莫耳%時,可能會出現伸長率、脆性、強度等機械性能降低的問題。另一方面,當咪唑基化合物的含量過多時,例如:當咪唑類化合物的含量大於40莫耳%時,聚醯胺酸組合物可能會具有較差的儲存穩定性。In addition, in the present disclosure, based on 1 mol of the repeating unit of polyamine, the content of the imidazole compound may be 0.1 to 40 mol%. The lower limit of the ratio may be, for example, 0.5 mol%, 1.0 mol%, 1.5 mol%, 2 mol%, 2.5 mol%, 3 mol%, 3.5 mol%, 4.0 mol%, 4.5 mol%, 4.7 mol%, 4.9 mol%, 5.0 mol%, 5.2 mol%, 5.5 mol%, 6.0 mol%, 6.5 mol%, 7.0 mol%, 7.5 mol%, 8.0 mol%, 8.5 mol%, 9.0 mol%, 9.5 mol%, or 10 mol% or more, and the upper limit of the ratio may be, for example, 35 mol%, 30 mol%, 28 mol%, 26 mol%, 24 mol%, 22 mol%, 20 mol%, 18 mol%, 15 mol%, 12 mol%, or 10 mol% or less. When the content of the imidazole compound is too low, for example, when the content of the imidazole compound is less than 0.1 mol%, the mechanical properties such as elongation, brittleness, and strength may be reduced. On the other hand, when the content of the imidazole compound is too high, for example, when the content of the imidazole compound is greater than 40 mol%, the polyamine composition may have poor storage stability.
在本揭露中,環氧基化合物(epoxy-based)為多官能環氧化合物。多官能環氧化合物可包括具有2至4個環氧官能基的環氧化合物,例如N,N'-N,N'-四縮水甘油基二氨基二苯甲烷(N,N'-tetraglycidyl diamino diphenyl methane, TGDDM)、雙酚A二縮水甘油醚(bisphenol A diglycidyl ether, DGEBA)、四縮水甘油基-間苯二甲胺(tetraglycidyl-meta-xylenediamine)、四縮水甘油基-1,3-雙胺基甲環己烷(tetraglycidyl-1,3-bisaminomethylcyclohexane)、以及三羥甲基丙烷三缩水甘油醚(trimethylolpropane triglycidyl ether, TMP)等,且優選地可為TGDDM。本揭露製備的聚醯胺酸組合物含有環氧基化合物作為添加劑,因此能夠提高交聯密度以具有剛性的機械性能。In the present disclosure, epoxy-based compounds are multifunctional epoxy compounds. The multifunctional epoxy compounds may include epoxy compounds having 2 to 4 epoxy functional groups, such as N,N'-N,N'-tetraglycidyl diamino diphenyl methane (TGDDM), bisphenol A diglycidyl ether (DGEBA), tetraglycidyl-meta-xylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, and trimethylolpropane triglycidyl ether (TMP), and preferably TGDDM. The polyamine composition prepared in the present disclosure contains an epoxy compound as an additive, so that the crosslinking density can be increased to have rigid mechanical properties.
此外,在本揭露中,以1莫耳聚醯胺酸之重複單元為基準,環氧基化合物的含量可為0.01至1.0莫耳%。該比例的下限可以是,例如0.02莫耳%、0.03莫耳%、0.05莫耳%、0.07莫耳%、或0.09莫耳%或更多,而其比例的上限可以是,例如0.9莫耳%、0.85 莫耳%、0.8莫耳%、0.75莫耳%、0.7莫耳%、0.65莫耳%、0.6莫耳%、0.55莫耳%、0.5莫耳%、0.48莫耳%、0.45莫耳%、0.4莫耳%、0.35莫耳%、或0.3莫耳%或更少。In addition, in the present disclosure, based on 1 mol of repeating units of polyamide, the content of epoxy compound can be 0.01 to 1.0 mol%. The lower limit of the ratio can be, for example, 0.02 mol%, 0.03 mol%, 0.05 mol%, 0.07 mol%, or 0.09 mol% or more, and the upper limit of the ratio can be, for example, 0.9 mol%, 0.85 mol%, 0.8 mol%, 0.75 mol%, 0.7 mol%, 0.65 mol%, 0.6 mol%, 0.55 mol%, 0.5 mol%, 0.48 mol%, 0.45 mol%, 0.4 mol%, 0.35 mol%, or 0.3 mol% or less.
在本揭露中,聚醯亞胺的強度可以藉由添加環氧基化合物來提高。然而,以1莫耳聚醯胺酸之重複單元為基準,當環氧基化合物的含量小於0.01莫耳%時,由於添加環氧基化合物而提高聚醯亞胺強度的效果可能會不顯著。當其含量大於1.0莫耳%時,由於互溶性降低,因此物理性能可能會降低。In the present disclosure, the strength of polyimide can be improved by adding an epoxy compound. However, based on 1 mol of repeating units of polyamide, when the content of the epoxy compound is less than 0.01 mol%, the effect of improving the strength of polyimide by adding the epoxy compound may not be significant. When the content is greater than 1.0 mol%, the physical properties may be reduced due to reduced solubility.
本揭露的聚醯胺酸組合物可以在聚醯胺酸中同時包含咪唑基化合物和環氧基化合物,因此可以預期其同時具有高強度和優異的伸長率。特別是本揭露的聚醯亞胺藉由在特定的二酐單體和二胺單體與咪唑基化合物混合時,促進亞胺化而表現出高強度和優異的伸長率以及改進的耐熱性和黃化指數。此外,藉由含有如TGDDM的環氧基化合物而進一步提高了伸長率,因此實現了聚醯亞胺具有改善的機械性能,且同時具有適合作為顯示基板材料之優異的熱特性。The polyamide composition disclosed herein can contain both an imidazole compound and an epoxy compound in the polyamide, so it can be expected to have high strength and excellent elongation at the same time. In particular, the polyimide disclosed herein exhibits high strength and excellent elongation as well as improved heat resistance and yellowing index by promoting imidization when a specific dianhydride monomer and a diamine monomer are mixed with an imidazole compound. In addition, the elongation is further improved by containing an epoxy compound such as TGDDM, thereby achieving polyimide with improved mechanical properties and excellent thermal properties suitable for being a display substrate material.
在本揭露中,有機溶劑只要是可以溶解聚醯胺酸、咪唑基化合物和環氧基化合物的有機溶劑就沒有特別限制,但可以是,例如非質子極性溶劑(aprotic polar solvent),優選地,作為有機溶劑N-甲基吡咯烷酮(N-methyl-pyrrolidone, NMP)、N,N'-二甲基甲醯胺(N,N'-dimethylformamide, DMF)、N,N'-二乙基甲醯胺(N,N'-diethylformamide, DEF)、N,N'-二甲基乙醯胺(N,N'-dimethylacetamide, DMAc)、二甲基丙醯胺(dimethylpropanamide, DMPA)、N,N-二乙基乙醯胺(685-91-6, N,N-diethylacetamide, DEAc)、以及3-甲氧基-N,N-二甲基丙醯胺(53185-52-7, 3-methoxy-N,N-dimethylpropanamide, KJCMPA)等其中一種或前述之組合,但最優選地可以使用NMP。In the present disclosure, the organic solvent is not particularly limited as long as it can dissolve the polyamine, the imidazole compound and the epoxy compound, but can be, for example, an aprotic polar solvent, preferably, as the organic solvent, N-methyl-pyrrolidone (NMP), N,N'-dimethylformamide (DMF), N,N'-diethylformamide (DEF), N,N'-dimethylacetamide (DMAc), dimethylpropanamide (DMPA), N,N-diethylacetamide (685-91-6, N,N-diethylacetamide, DEAc), and 3-methoxy-N,N-dimethylpropanamide (53185-52-7, 3-methoxy-N,N-dimethylpropanamide, KJCMPA) or a combination thereof, but NMP is most preferably used.
在本揭露中,本揭露製備的聚醯胺酸組合物可具有1,000克/莫耳至100,000克/莫耳的重量平均分子量。重量平均分子量的下限可以1,500克/莫耳、2,000克/莫耳、2,500克/莫耳、或3,000克/莫耳或更高,而重量平均分子量的上限可以90,000克/莫耳、80,000克/摩爾、70,000克/摩爾、60,000克/莫耳、50,000克/莫耳、30,000克/莫耳、29,000克/莫耳、或28,500克/莫耳或更低。In the present disclosure, the polyamine composition prepared in the present disclosure may have a weight average molecular weight of 1,000 g/mol to 100,000 g/mol. The lower limit of the weight average molecular weight may be 1,500 g/mol, 2,000 g/mol, 2,500 g/mol, or 3,000 g/mol or higher, and the upper limit of the weight average molecular weight may be 90,000 g/mol, 80,000 g/mol, 70,000 g/mol, 60,000 g/mol, 50,000 g/mol, 30,000 g/mol, 29,000 g/mol, or 28,500 g/mol or lower.
在本揭露中,本揭露製備的聚醯胺酸組合物可具有5wt%至30wt%的固含量。固含量之重量百分比的下限可以是5wt%、8wt%、9wt%、10wt%、15wt%、20wt%、21wt%、22wt%、23 wt%、24wt%、25wt%、26wt%、27wt%、28wt%、或29 wt%或更多,而固含量之重量百分比的上限可以是29wt%、27 wt%、25wt%、23wt%、21wt%、20wt%、19wt%、或18 wt% 或更少。藉由調整聚醯胺酸組合物的固含量,可以控制黏度的增加並縮短固化製程中的製程時間。In the present disclosure, the polyamide composition prepared in the present disclosure may have a solid content of 5wt% to 30wt%. The lower limit of the weight percentage of the solid content may be 5wt%, 8wt%, 9wt%, 10wt%, 15wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, or 29wt% or more, and the upper limit of the weight percentage of the solid content may be 29wt%, 27wt%, 25wt%, 23wt%, 21wt%, 20wt%, 19wt%, or 18wt% or less. By adjusting the solid content of the polyamide composition, the increase in viscosity can be controlled and the process time in the curing process can be shortened.
在本揭露中,聚醯胺酸組合物的黏度可在1,000釐泊至10,000釐泊的範圍,所述黏度是在23℃的溫度以及1s -1的剪率下測量。例如,黏度的上限可以是10,000釐泊、8,000釐泊、5,000釐泊、4,700釐泊、4,500釐泊、4,000釐泊、3,800釐泊、3,700釐泊、3,500釐泊、3,300釐泊、3,200釐泊、3,100釐泊、或3,000釐泊或更少,而其下限沒有特別限制,但可以是1,200釐泊、1,500釐泊、2,000釐泊、或2,500釐泊或更高。可以使用例如賽默飛世爾科技(Thermo Fisher Scientific Inc.)製造的哈克600流變儀(Haake Rheostress 600)來測量黏度,且在剪率為1s -1、溫度為23℃、平板間隙為1毫米的條件下進行測量。本揭露可藉由調整黏度範圍提供具有優異加工性能的前驅組合物。 In the present disclosure, the viscosity of the polyamino acid composition may be in the range of 1,000 to 10,000 millipoise, which is measured at a temperature of 23° C. and a shear rate of 1 s −1 . For example, the upper limit of the viscosity may be 10,000, 8,000, 5,000, 4,700, 4,500, 4,000, 3,800, 3,700, 3,500, 3,300, 3,200, 3,100, or 3,000 or less, and the lower limit thereof is not particularly limited but may be 1,200, 1,500, 2,000, or 2,500 or more. The viscosity can be measured using, for example, a Haake Rheostress 600 manufactured by Thermo Fisher Scientific Inc., and the measurement is performed under the conditions of a shear rate of 1 s -1 , a temperature of 23° C., and a plate gap of 1 mm. The present disclosure can provide a precursor composition with excellent processing properties by adjusting the viscosity range.
此外,本揭露提供一種聚醯亞胺,其為上述聚醯胺酸組合物的固化物,聚醯亞胺可以製備成用於物理性質分析的薄膜狀。In addition, the present disclosure provides a polyimide, which is a cured product of the polyamic acid composition. The polyimide can be prepared into a film for physical property analysis.
因此,在本揭露的另一個面向,提供了一種包含所述聚醯胺酸組合物之固化產物的聚醯亞胺薄膜。Therefore, in another aspect of the present disclosure, a polyimide film comprising a cured product of the polyamic acid composition is provided.
在本揭露中,除了主要用作判斷聚醯亞胺熱性能之標準的熱膨脹係數(coefficient of thermal expansion, CTE)和熱分解溫度(glass transition temperature, Td)之外,玻璃轉化溫度(thermal decomposition temperature, Tg)能夠在預測熱性能的同時,還確保機械性能,這一點得到了證實。In the present disclosure, it is confirmed that the glass decomposition temperature (Tg) can ensure mechanical properties while predicting thermal properties, in addition to the coefficient of thermal expansion (CTE) and the glass transition temperature (Td), which are mainly used as criteria for judging the thermal properties of polyimide.
在本揭露中,聚醯胺酸可具有在3ppm/℃至20ppm/℃的範圍的熱膨脹係數,例如,熱膨脹係數的上限可以是19ppm/℃、18ppm/℃、16ppm/℃、14ppm/℃、12ppm/℃、10ppm/℃、或8 ppm/℃或更小,而其下限可以是,例如4ppm/℃、4.5ppm/℃、5.0ppm/℃、5.5ppm/℃、6.0ppm/℃、6.5ppm/℃、或7ppm/℃或更大。在一個實施例中,熱膨脹係數可以在100℃至400℃下測量。對於熱膨脹係數的測量,可以使用由美商沃特斯台灣分公司(TA Instruments)製造的熱力學分析儀 Q400 型號。具體而言,可以藉由將聚醯亞胺製成薄膜,將薄膜切割成寬2毫米和長10毫米的尺寸,接著在氮氣氣氛中對聚醯亞胺薄膜施加0.05牛頓的張力來確定熱膨脹係數,藉由以10℃/分鐘的速率將溫度從室溫升至400℃,接著再次以 10℃/分鐘的速率冷卻,從而測量從100℃到350℃區段的斜率。In the present disclosure, polyamide may have a thermal expansion coefficient in the range of 3ppm/°C to 20ppm/°C, for example, the upper limit of the thermal expansion coefficient may be 19ppm/°C, 18ppm/°C, 16ppm/°C, 14ppm/°C, 12ppm/°C, 10ppm/°C, or 8ppm/°C or less, and the lower limit thereof may be, for example, 4ppm/°C, 4.5ppm/°C, 5.0ppm/°C, 5.5ppm/°C, 6.0ppm/°C, 6.5ppm/°C, or 7ppm/°C or more. In one embodiment, the thermal expansion coefficient may be measured at 100°C to 400°C. For the measurement of the thermal expansion coefficient, a thermodynamic analyzer Q400 manufactured by TA Instruments, Inc., may be used. Specifically, the thermal expansion coefficient can be determined by making polyimide into a film, cutting the film into a size of 2 mm wide and 10 mm long, and then applying a tension of 0.05 Newton to the polyimide film in a nitrogen atmosphere, and measuring the slope of the section from 100°C to 350°C by increasing the temperature from room temperature to 400°C at a rate of 10°C/min and then cooling again at a rate of 10°C/min.
此外,在本揭露中,聚醯胺酸組合物的玻璃轉化溫度可在370℃的範圍或更高,例如,玻璃轉化溫度的下限可以是375℃、380℃、385℃、或390℃或更高,而玻璃轉化溫度的上限可以是600℃或更低。玻璃化轉變溫度可以使用熱力學分析儀以10℃/分鐘對藉由固化聚醯胺酸組合物製備的聚醯亞胺進行測量。In addition, in the present disclosure, the glass transition temperature of the polyamine composition may be in the range of 370° C. or higher, for example, the lower limit of the glass transition temperature may be 375° C., 380° C., 385° C., or 390° C. or higher, and the upper limit of the glass transition temperature may be 600° C. or lower. The glass transition temperature can be measured at 10° C./min on a polyimide prepared by curing the polyamine composition using a thermodynamic analyzer.
在本揭露中,藉由固化聚醯胺酸組合物獲得的聚醯亞胺可具有470℃或更高之損失5wt%的熱分解溫度。熱分解溫度可以使用美商沃特斯台灣分公司(TA Instruments)製造的熱重分析儀(Q50)測量。在一個具體的例示中,將聚醯胺酸組合物固化得到的聚醯亞胺在氮氣氣氛中以10℃/分鐘的速率加熱到150℃,然後持溫30分鐘以去除水分,接著,可以 10℃/分鐘的速率將溫度升高到 600℃,以測量發生5wt%重量損失時的溫度。熱分解溫度的下限可以是,例如470℃、475℃、480℃、482℃、484℃、486℃、488℃、490℃、492℃、494℃、496℃、498℃、 500℃、505℃、506℃、507℃、508℃、509℃、或510℃或更高,而其上限可以是,例如800℃、750℃、700℃、650℃、630℃、或600℃或更低。In the present disclosure, the polyimide obtained by curing the polyamic acid composition may have a thermal decomposition temperature of 470°C or higher at a loss of 5 wt%. The thermal decomposition temperature can be measured using a thermogravimetric analyzer (Q50) manufactured by TA Instruments, Inc., Taiwan, USA. In a specific example, the polyimide obtained by curing the polyamic acid composition is heated to 150°C at a rate of 10°C/min in a nitrogen atmosphere, and then kept at this temperature for 30 minutes to remove moisture, and then the temperature can be raised to 600°C at a rate of 10°C/min to measure the temperature at which 5 wt% weight loss occurs. The lower limit of the thermal decomposition temperature can be, for example, 470°C, 475°C, 480°C, 482°C, 484°C, 486°C, 488°C, 490°C, 492°C, 494°C, 496°C, 498°C, 500°C, 505°C, 506°C, 507°C, 508°C, 509°C, or 510°C or higher, and the upper limit thereof can be, for example, 800°C, 750°C, 700°C, 650°C, 630°C, or 600°C or lower.
此外,使聚醯胺酸組合物固化而得到之聚醯亞胺的伸長率為6%或更高,例如7%、8%、9%、10%或更高,而伸長率的上限沒有特別限制,但可為40%以下。伸長率可以藉由將聚醯胺酸組合物固化成聚醯亞胺薄膜,將聚醯亞胺薄膜切割成寬10毫米和長40毫米的尺寸,接著使用來自英斯特朗公司(Instron Corp)的Instron5564 UTM設備並藉由ASTM D-882方法來測定伸長率。In addition, the elongation of the polyimide obtained by curing the polyamic acid composition is 6% or more, such as 7%, 8%, 9%, 10% or more, and the upper limit of the elongation is not particularly limited, but may be 40% or less. The elongation can be measured by curing the polyamic acid composition into a polyimide film, cutting the polyimide film into a size of 10 mm wide and 40 mm long, and then using an Instron 5564 UTM device from Instron Corp. and measuring the elongation by ASTM D-882 method.
在本揭露中,將聚醯胺酸組合物固化得到的薄膜狀聚醯亞胺具有10±0.5微米的厚度,測定黃化指數(yellow index, YI)時,黃化指數為10以下,優選地為 7或更小,更優選地為5或更小,還更優選地為3.5或更小。在將聚醯亞胺薄膜用於顯示器用基板等透光部時,聚醯亞胺薄膜需要具有透明性,更準確地說是無色(無彩色)透明性。這表示黃化指數的絕對值越小,薄膜的顏色越接近無色(無彩)。如果黃化指數為10或更小,特別優選地為5或更小,當在10±0.5微米的薄膜厚度下測量時,可以確保一般所需的無色。此外,隨著薄膜厚度的增加,黃化指數亦趨向增加。再者,黃化指數優選地為0或更大。In the present disclosure, the film-like polyimide obtained by curing the polyamic acid composition has a thickness of 10±0.5 microns, and when the yellowing index (YI) is measured, the yellowing index is 10 or less, preferably 7 or less, more preferably 5 or less, and more preferably 3.5 or less. When the polyimide film is used in a light-transmitting portion such as a display substrate, the polyimide film needs to have transparency, more precisely, colorless (achromatic) transparency. This means that the smaller the absolute value of the yellowing index, the closer the color of the film is to colorless (achromatic). If the yellowing index is 10 or less, particularly preferably 5 or less, when measured at a film thickness of 10±0.5 microns, the generally required colorlessness can be ensured. In addition, as the film thickness increases, the yellowing index also tends to increase. Furthermore, the yellowing index is preferably 0 or greater.
在本揭露中,對於藉由固化聚醯胺酸組合物獲得之聚醯亞胺的強度,強度的提高程度可以藉由固定具有50毫米寬度、50毫米長度以及厚度為10±0.5微米的聚醯亞胺薄膜來測量,反覆折疊和彎曲薄膜,且以肉眼觀察裂紋和斷裂以確認根據折疊次數之裂紋和斷裂的程度。In the present disclosure, with respect to the strength of polyimide obtained by curing a polyamic acid composition, the degree of improvement in strength can be measured by fixing a polyimide film having a width of 50 mm, a length of 50 mm, and a thickness of 10±0.5 μm, repeatedly folding and bending the film, and visually observing cracks and breaks to confirm the extent of cracks and breaks according to the number of folding times.
在本揭露的另一個面向,提供了一種聚醯胺酸組合物,其包括:聚醯胺酸,包括,作為一聚合單元,由化學式1所示的二酐單體以及由化學式2的二胺單體: [化學式1] [化學式2] 2-苯基咪唑;N-甲基吡咯烷酮(NMP)以及N,N'-四縮水甘油基二氨基二苯甲烷(TGDDM)。 In another aspect of the present disclosure, a polyamine composition is provided, comprising: a polyamine, comprising, as a polymerizable unit, a dianhydride monomer represented by Chemical Formula 1 and a diamine monomer represented by Chemical Formula 2: [Chemical Formula 1] [Chemical formula 2] 2-phenylimidazole; N-methylpyrrolidone (NMP) and N,N'-tetraglycidyldiaminodiphenylmethane (TGDDM).
作為咪唑基化合物之2-苯基咪唑和作為環氧類化合物之TGDDM的含量與前述相同。The contents of 2-phenylimidazole as the imidazole compound and TGDDM as the epoxy compound are the same as described above.
在本揭露的又一個面向,提供了一種聚醯胺酸組合物,其包括:聚醯胺酸,包括,作為一聚合單元,由化學式1所示的二酐單體以及由化學式2或化學式3的二胺單體: [化學式1] [化學式2] [化學式3] 2-苯基咪唑;N-甲基吡咯烷酮(NMP)以及N,N'-四縮水甘油基二氨基二苯甲烷(TGDDM)。 In another aspect of the present disclosure, a polyamine composition is provided, comprising: a polyamine, comprising, as a polymerizing unit, a dianhydride monomer represented by Chemical Formula 1 and a diamine monomer represented by Chemical Formula 2 or Chemical Formula 3: [Chemical Formula 1] [Chemical formula 2] [Chemical formula 3] 2-phenylimidazole; N-methylpyrrolidone (NMP) and N,N'-tetraglycidyldiaminodiphenylmethane (TGDDM).
此處,在總二胺單體成分中可包括90莫耳%之由化學式2所示的二胺單體和10莫耳%之由化學式3所示的二胺單體。Here, 90 mol% of the diamine monomer represented by Chemical Formula 2 and 10 mol% of the diamine monomer represented by Chemical Formula 3 may be included in the total diamine monomer component.
此外,作為咪唑基化合物之2-苯基咪唑和作為環氧類化合物之TGDDM的含量與前述相同。In addition, the contents of 2-phenylimidazole as the imidazole compound and TGDDM as the epoxy compound are the same as described above.
在本揭露的又一個面向,本揭露製備的聚醯胺酸組合物可包括:具有由化學式5所示之重複單元的聚醯胺酸;咪唑基化合物;環氧基化合物;以及有機溶劑: [化學式5] 在化學式5中,R 1和R 2為相同或不同,且各自獨立表示氫原子、C 1-C 6烷基或C 3-C 9烷基甲矽烷基; 在化學式5所示之聚醯胺酸的整個重複單元中,70莫耳%或更多、優選地80莫耳%或更多、更優選地90mol%或更多,甚至更優選地100莫耳%的A部分是由化學式1所示之二酐單體的衍生結構;以及 [化學式1] 在由化學式5所示之聚醯胺酸的整個重複單元中,W部分是由化學式2及/或化學式3所示之二胺單體的衍生結構。此處,70莫耳%或更多、優選地80莫耳%或更多、以及更優選地90莫耳%或更多的W部分是由化學式2所示之二胺單體的衍生結構: [化學式2] [化學式3] In another aspect of the present disclosure, the polyamine composition prepared in the present disclosure may include: a polyamine having a repeating unit represented by Chemical Formula 5; an imidazole compound; an epoxy compound; and an organic solvent: [Chemical Formula 5] In Chemical Formula 5, R1 and R2 are the same or different and each independently represents a hydrogen atom, a C1 - C6 alkyl group or a C3 - C9 alkylsilyl group; In the entire repeating unit of the polyamide represented by Chemical Formula 5, 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, and even more preferably 100 mol% of the A portion is a structure derived from the dianhydride monomer represented by Chemical Formula 1; and [Chemical Formula 1] In the entire repeating unit of the polyamine represented by Chemical Formula 5, the W portion is a derivative structure of a diamine monomer represented by Chemical Formula 2 and/or Chemical Formula 3. Here, 70 mol% or more, preferably 80 mol% or more, and more preferably 90 mol% or more of the W portion is a derivative structure of a diamine monomer represented by Chemical Formula 2: [Chemical Formula 2] [Chemical formula 3]
咪唑基化合物、環氧基化合物和有機溶劑的種類以及含量與前述相同。The types and contents of the imidazole compound, epoxy compound and organic solvent are the same as those described above.
藉由測量具有重量百分比損失的熱分解溫度、熱膨脹係數和玻璃化轉變溫度,證實了根據本揭露的聚醯亞胺具有適合應用於顯示基板的低黃化指數水準,且保持了聚醯亞胺特有的優異熱性能。此外,藉由伸長率測量和脆性分析表明,根據本揭露的聚醯亞胺具有高強度,且同時保持優異的伸長率。By measuring the thermal decomposition temperature, thermal expansion coefficient and glass transition temperature with weight percentage loss, it is confirmed that the polyimide according to the present disclosure has a low yellowing index level suitable for application in display substrates and maintains the excellent thermal properties unique to polyimide. In addition, by elongation measurement and brittleness analysis, it is shown that the polyimide according to the present disclosure has high strength and maintains excellent elongation at the same time.
確認根據本揭露之最佳聚醯胺酸組合物的成分和含量以實現適用於如上所述之顯示基板的熱性能、機械性能以及透明性。The composition and content of the optimal polyamine composition according to the present disclosure are determined to achieve thermal properties, mechanical properties and transparency suitable for the display substrate as described above.
因此,根據本揭露的聚醯胺酸組合物和用其製備的聚醯亞胺可利於使用在如顯示器基板的基板中。Therefore, the polyamic acid composition and the polyimide prepared therefrom according to the present disclosure can be advantageously used in substrates such as display substrates.
在本揭露的又一個面向,本揭露提供了一種可撓性顯示器,其包括所述聚醯亞胺薄膜作為基板,而聚醯亞胺薄膜由前述聚醯胺酸組合物製備而成。In another aspect of the present disclosure, the present disclosure provides a flexible display, which includes the polyimide film as a substrate, and the polyimide film is prepared from the polyamic acid composition.
[有利效果] 根據本揭露的聚醯胺酸組合物以及包含聚醯胺酸組合物的聚醯亞胺,可以具有優異的機械性能,例如強度和伸長率,同時保持低黃化指數和優異的熱性能。 [Advantageous Effects] The polyamine composition and the polyimide containing the polyamine composition disclosed herein can have excellent mechanical properties, such as strength and elongation, while maintaining a low yellowing index and excellent thermal properties.
以下提供例示以幫助理解本揭露。為了更容易理解本揭露,提供以下實施例,而本揭露的內容不受這些實施例的限制。The following examples are provided to help understand the present disclosure. In order to make it easier to understand the present disclosure, the following embodiments are provided, but the content of the present disclosure is not limited to these embodiments.
<< 聚Gather 醯Acetyl 胺酸組合物的製備Preparation of amino acid compositions >>
實施例Embodiment 11 :聚: Poly 醯Acetyl 胺酸組合物Amino acid combination
將DABAN和N-甲基-2-吡咯烷酮放入充滿氮氣的反應容器中,混合物在50℃的溫度下攪拌1小時。緩慢加入CpODA至攪拌溶液中,在室溫下攪拌4小時或更多,並反應至黏度沒有變化,從而獲得聚醯胺酸。DABAN and N-methyl-2-pyrrolidone were placed in a reaction vessel filled with nitrogen, and the mixture was stirred at 50°C for 1 hour. CpODA was slowly added to the stirred solution, stirred at room temperature for 4 hours or more, and reacted until the viscosity did not change, thereby obtaining polyamine.
以1莫耳該聚醯胺酸之重複單元為基準,添加20莫耳%之2-苯基咪唑作為咪唑基化合物,且以1莫耳該聚醯胺酸之重複單元為基準,添加0.08莫耳%之TGDDM作為用作交聯劑的環氧基合物。接著,將所得混合物在室溫下攪拌3小時並反應至黏度沒有變化,由此製備聚醯胺酸組合物。Based on 1 mol of the repeating unit of the polyamide, 20 mol% of 2-phenylimidazole was added as an imidazole compound, and based on 1 mol of the repeating unit of the polyamide, 0.08 mol% of TGDDM was added as an epoxy compound used as a crosslinking agent. Then, the obtained mixture was stirred at room temperature for 3 hours and reacted until the viscosity did not change, thereby preparing a polyamide composition.
實施例Embodiment 22 至to 1111 :聚: Poly 醯Acetyl 胺酸組合物Amino acid combination
如表1所示,用與實施例1同樣的方法製備聚醯胺酸組合物,除了單體成分及其含量比例,對咪唑基化合物的含量比例以及環氧基化合物的含量比例進行了調整。As shown in Table 1, the polyamine composition was prepared in the same manner as in Example 1, except that the content ratio of the imidazole compound and the content ratio of the epoxy compound were adjusted in addition to the monomer components and their content ratios.
[表1]
以下各種實施例中使用的化合物之簡稱如下所示。 降冰片烷-2-螺-α-環戊酮-α′-螺-2″-降冰片烷-5,5″,6,6″-四羧酸二酐:CpODA 4,4'-二氨基苯甲醯苯胺:DABAN N,N'-雙(4-氨基苯基)苯-1,4-二甲醯胺:DATA N-甲基吡咯烷酮:NMP The abbreviations of the compounds used in the following various examples are as follows. Norbornane-2-spiro-α-cyclopentanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride: CpODA 4,4'-diaminobenzanilide: DABAN N,N'-bis(4-aminophenyl)benzene-1,4-dimethylamide: DATA N-methylpyrrolidone: NMP
實驗實施例。由本揭露之聚Experimental Examples. 醯Acetyl 胺酸組合物所製備的聚醯亞胺之物理性能分析。Analysis of physical properties of polyimide prepared from amino acid composition.
<< 用於物理性能測量之聚醯亞胺的製備Preparation of polyimide for physical property measurement >>
從實施例1至11中製備的每個聚醯胺酸組合物中,藉由1,500rpm或更高的高速旋轉以去除氣泡。接著,使用旋塗機將每個消泡的聚醯胺酸組合物施加到玻璃基板上。From each of the polyamine compositions prepared in Examples 1 to 11, air bubbles were removed by high-speed spinning at 1,500 rpm or more. Then, each defoamed polyamine composition was applied to a glass substrate using a spin coater.
在氮氣氣氛中,以4℃/分鐘的速度從室溫升溫至400℃,產品在400℃熱處理60分鐘,接著以4℃/分鐘的速度降溫至30℃,從而得到10±0.5微米的薄膜狀聚醯亞胺。In a nitrogen atmosphere, the temperature was raised from room temperature to 400°C at a rate of 4°C/min, the product was heat treated at 400°C for 60 minutes, and then cooled to 30°C at a rate of 4°C/min, thereby obtaining a 10±0.5 μm thin film of polyimide.
實驗實施例Experimental Examples 11 :厚度量測:Thickness measurement
根據前述實施例製備之聚醯亞胺的厚度使用由安立知公司(Anritsu Corporation)製造的電膜厚度測試儀測量。The thickness of the polyimide prepared according to the aforementioned embodiment was measured using a film thickness tester manufactured by Anritsu Corporation.
實驗實施例Experimental Examples 22 :黏度量測:Viscosity measurement
對於實施例中製備的聚醯胺酸組合物,使用賽默飛世爾科技(Thermo Fisher Scientific Inc.)製造的哈克600流變儀(Haake Rheostress 600),且在剪率為1s -1、溫度為23℃、平板間隙為1毫米的條件下來測量黏度。 For the polyamine composition prepared in the example, the viscosity was measured using a Haake Rheostress 600 manufactured by Thermo Fisher Scientific Inc. under the conditions of a shear rate of 1 s -1 , a temperature of 23° C., and a plate gap of 1 mm.
實驗實施例Experimental Examples 33 :黃化指數量測:Yellowing index measurement
對於根據前述實施例製備的聚醯亞胺,黃化指數使用來自亨特聯合實驗室(Hunter Lab)的色度計測量。For the polyimide prepared according to the aforementioned examples, the yellowing index was measured using a colorimeter from Hunter Lab.
實驗實施例Experimental Examples 44 :具有重量百分比損失的熱分解溫度: Thermal decomposition temperature with weight percentage loss (( Thermal Decomposition Temperature, TdThermal Decomposition Temperature, Td ))
使用由美商沃特斯台灣分公司(TA Instruments)製造的熱重分析儀Q50型號,將聚醯亞胺薄膜在氮氣環境中以10℃/分鐘的速率加熱至150℃,然後持溫30分鐘以去除水分。接著以10℃/分鐘的速度升溫至600℃,測定重量損失5%時的溫度。Using a thermogravimetric analyzer Q50 manufactured by TA Instruments, the polyimide film was heated to 150°C in a nitrogen atmosphere at a rate of 10°C/min, then kept at that temperature for 30 minutes to remove moisture. The temperature was then raised to 600°C at a rate of 10°C/min, and the temperature at which the weight loss was 5% was measured.
實驗實施例Experimental Examples 55 :熱膨脹係數(: Thermal expansion coefficient ( Coefficient of Thermal Expansion , CTECoefficient of Thermal Expansion , CTE )量測) Measurement
使用由美商沃特斯台灣分公司(TA Instruments)製造的熱機械分析儀 Q400 型號。具體而言,將薄膜狀聚醯亞胺裁切成寬2毫米和長10毫米的大小。在氮氣氣氛中對聚醯亞胺薄膜施加0.05牛頓張力,以10℃/分鐘的速率從室溫升至400℃,接著以10℃/分鐘的速率再次冷卻,從而測量100℃到350℃的截面斜率。A thermomechanical analyzer Q400 manufactured by TA Instruments was used. Specifically, a thin film of polyimide was cut into a size of 2 mm in width and 10 mm in length. A tension of 0.05 Newton was applied to the polyimide film in a nitrogen atmosphere, and the temperature was increased from room temperature to 400°C at a rate of 10°C/min, and then cooled again at a rate of 10°C/min, thereby measuring the cross-sectional slope from 100°C to 350°C.
實驗實施例Experimental Examples 66 :玻璃化轉變溫度(: Glass transition temperature ( Glass Transition Temperature, TgGlass Transition Temperature, Tg ))
對於實施例之聚醯胺酸組合物製備的聚醯亞胺薄膜,使用熱機械分析儀(thermomechanical analyzer, TMA)以10℃/分鐘條件下的快速膨脹點作為起始點來測量。The polyimide film prepared from the polyamic acid composition of the example was measured using a thermomechanical analyzer (TMA) with the rapid expansion point at 10° C./min as the starting point.
實驗實施例Experimental Examples 77 :伸長率: Elongation
將實施例之聚醯胺酸組合物製備的聚醯亞胺薄膜切割成寬10毫米和長40毫米的尺寸,並使用來自英斯特朗公司(Instron Corp)的Instron5564 UTM設備並藉由ASTM D-882方法來測定伸長率。The polyimide film prepared from the polyamic acid composition of the example was cut into a size of 10 mm in width and 40 mm in length, and the elongation was measured using an Instron 5564 UTM apparatus from Instron Corp. according to the ASTM D-882 method.
實驗實施例Experimental Examples 88 :強度分析:Intensity analysis
對於實施例之聚醯胺酸組合物製備的聚醯亞胺薄膜,將聚醯亞胺薄膜切成寬50毫米和長50毫米的尺寸(厚度10毫米),藉由對齊薄膜的兩端,反覆折疊(180°)和彎曲薄膜,並用肉眼觀察裂紋和斷裂來分析每個聚醯亞胺薄膜的強度。將薄膜折疊 5 次或以上,將沒有裂紋和斷裂的情況判定為 A+,將其折疊 5 次或以上但有小裂紋的情況判定為 A-,最多可折疊3次,但如果在隨後的折疊中斷裂,則判定為B+,以及最多可以折疊2次,但如果在隨後的折疊中斷裂,則判定為B-。For the polyimide film prepared from the polyamic acid composition of the embodiment, the polyimide film was cut into a size of 50 mm in width and 50 mm in length (thickness 10 mm), and the strength of each polyimide film was analyzed by aligning the two ends of the film, repeatedly folding (180°) and bending the film, and observing cracks and breaks with the naked eye. The film was folded 5 times or more, and the case where there were no cracks and breaks was judged as A+, and the case where it was folded 5 times or more but had small cracks was judged as A-, and it could be folded up to 3 times, but if it broke in the subsequent folding, it was judged as B+, and it could be folded up to 2 times, but if it broke in the subsequent folding, it was judged as B-.
[表2]
說明書中省略了本揭露所屬技術領域中具有通常知識者能夠充分認識和推知的細節。除了本說明書中描述的具體例示之外,可以在不改變本揭露的技術精神或基本架構的範圍內進行各種修改。因此,本揭露可以不同於本文具體描述和說明的方式實施,本揭露所屬技術領域中具有通常知識者將理解這些方式。The specification omits details that can be fully recognized and inferred by a person skilled in the art to which the present disclosure belongs. In addition to the specific examples described in the specification, various modifications can be made within the scope of not changing the technical spirit or basic structure of the present disclosure. Therefore, the present disclosure can be implemented in a manner different from that specifically described and illustrated herein, and a person skilled in the art to which the present disclosure belongs will understand these manners.
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