TW202417546A - Polyimide film, flexible metal foil clad laminate and electronic component comprising the same - Google Patents
Polyimide film, flexible metal foil clad laminate and electronic component comprising the same Download PDFInfo
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 110
- 229910052751 metal Inorganic materials 0.000 title claims description 20
- 239000002184 metal Substances 0.000 title claims description 20
- 239000011888 foil Substances 0.000 title claims description 19
- 230000009477 glass transition Effects 0.000 claims abstract description 21
- 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 description 81
- 150000004985 diamines Chemical class 0.000 claims description 44
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000004642 Polyimide Substances 0.000 claims description 20
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 19
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 14
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical compound CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 claims description 13
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 8
- 229920001400 block copolymer Polymers 0.000 claims description 6
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 19
- 238000000034 method Methods 0.000 description 36
- 239000004952 Polyamide Substances 0.000 description 17
- 229920002647 polyamide Polymers 0.000 description 17
- 239000002904 solvent Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- 229920000768 polyamine Polymers 0.000 description 11
- 239000000945 filler Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000012024 dehydrating agents Substances 0.000 description 5
- 125000005462 imide group Chemical group 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 108010025899 gelatin film Proteins 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 125000006159 dianhydride group Chemical group 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920005575 poly(amic acid) Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229920006259 thermoplastic polyimide Polymers 0.000 description 2
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 description 1
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 1
- VZBRQINOYCAHGE-UHFFFAOYSA-N 4-amino-N-(4-aminophenyl)benzamide Chemical compound NC1=CC=C(C(=O)NC2=CC=C(C=C2)N)C=C1.NC1=CC=C(C(=O)NC2=CC=C(C=C2)N)C=C1 VZBRQINOYCAHGE-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- -1 diamine compound Chemical class 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
Abstract
本發明提供一種屈服強度為138 MPa以上、玻璃轉化溫度為370℃以上的耐熱性和機械特性優異的聚醯亞胺膜及其製造方法。The present invention provides a polyimide film having a yield strength of 138 MPa or more, a glass transition temperature of 370°C or more, excellent heat resistance and mechanical properties, and a method for producing the same.
Description
本發明係關於具有優異耐熱性和機械特性(屈服強度(yield strength)和屈服點(yield point))的聚醯亞胺膜及其製造方法。The present invention relates to a polyimide film having excellent heat resistance and mechanical properties (yield strength and yield point) and a method for producing the same.
聚醯亞胺(polyimide:PI)以剛性芳族主鏈和化學穩定性非常優異的醯亞胺環為基礎,是在有機材料中也具有最高水平的耐熱性、耐藥品性、電氣絕緣性、耐化學性、耐氣候性的高分子材料。Polyimide (PI) is based on a rigid aromatic main chain and an imide ring with excellent chemical stability. It is a polymer material that has the highest level of heat resistance, chemical resistance, electrical insulation, chemical resistance, and weather resistance among organic materials.
聚醯亞胺膜作為要求前述特性的多種電子設備的材料而倍受矚目。Polyimide films have attracted much attention as materials for various electronic devices requiring the above-mentioned properties.
應用聚醯亞胺膜的微電子部件可以例如電路積體度高的可撓性超薄電路基板,以便能夠應對電子製品的輕量化和小型化,聚醯亞胺膜尤其廣泛用作超薄電路基板的絕緣薄膜。Microelectronic components using polyimide films can be, for example, flexible ultra-thin circuit substrates with high circuit integration, so as to cope with the lightweight and miniaturization of electronic products. Polyimide films are particularly widely used as insulating films for ultra-thin circuit substrates.
前述超薄電路基板的結構一般是在絕緣薄膜上形成有包括金屬箔的電路,從廣義而言,將這種超薄電路基板稱為可撓性覆金屬箔層壓板(Flexible Metal Foil Clad Laminate),當使用薄銅板作為金屬箔時,從狹義而言,也稱為可撓性覆銅板(Flexible Copper Clad Laminate:FCCL)。The structure of the aforementioned ultra-thin circuit substrate is generally that a circuit including a metal foil is formed on an insulating film. In a broad sense, such an ultra-thin circuit substrate is called a flexible metal foil clad laminate (Flexible Metal Foil Clad Laminate). When a thin copper plate is used as the metal foil, in a narrow sense, it is also called a flexible copper clad laminate (Flexible Copper Clad Laminate: FCCL).
作為可撓性覆金屬箔層壓板的製造方法,可以例如:(i)在金屬箔上澆鑄(casting)或塗覆作為聚醯亞胺前驅物的聚醯胺酸後進行醯亞胺化的鑄造法;(ii)藉由濺射(Sputtering)而在聚醯亞胺膜上直接設置金屬層的金屬化法;以及(iii)藉由熱可塑性聚醯亞胺而以熱和壓力使聚醯亞胺膜與金屬箔接合的層壓法。As a method for manufacturing a flexible metal-clad laminate, for example: (i) a casting method in which polyamide as a polyimide precursor is cast or coated on a metal foil and then imidized; (ii) a metallization method in which a metal layer is directly provided on a polyimide film by sputtering; and (iii) a lamination method in which a polyimide film and a metal foil are bonded by heat and pressure using thermoplastic polyimide.
特別是金屬化法,例如在20 μm至38 μm厚度的聚醯亞胺膜上濺射銅等金屬而依次沉積黏接(Tie)層、種子(Seed)層,從而生產可撓性覆金屬箔層壓板的方法,在形成電路圖案的節距(pitch)為35 μm以下的超微電路方面具有優勢,正廣泛用於製造用於COF(chip on film:薄膜覆晶)的可撓性覆金屬箔層壓板。In particular, the metallization method, for example, sputtering a metal such as copper on a polyimide film with a thickness of 20 μm to 38 μm and depositing a tie layer and a seed layer in sequence to produce a flexible metal-clad laminate, has advantages in forming ultra-fine circuits with a pitch of less than 35 μm in the circuit pattern, and is widely used to manufacture flexible metal-clad laminates for COF (chip on film).
這種可撓性覆金屬箔層壓板所使用的聚醯亞胺膜需具有高耐熱性和機械特性,因而迫切要求優異的耐熱性和機械特性可以並存的聚醯亞胺膜。The polyimide film used in this flexible metal-clad laminate needs to have high heat resistance and mechanical properties, and thus there is an urgent need for a polyimide film that can have both excellent heat resistance and mechanical properties.
以上先前技術中記載的事項用於幫助對發明背景的理解,可以包括並非該技術領域的一般技藝人士已知的以往技術的事項。The matters described in the above prior art are used to help understanding the background of the invention and may include matters of the prior art that are not known to ordinary technicians in the technical field.
[先前技術文獻] [專利文獻] 專利文獻1:韓國授權專利第10-1375276號。 專利文獻2:韓國公開專利公報第2016-0002402號。 [Prior Art Documents] [Patent Documents] Patent Document 1: Korean Granted Patent No. 10-1375276. Patent Document 2: Korean Publication Patent Gazette No. 2016-0002402.
[技術課題][Technical topics]
因此,本發明目的在於提供一種同時具有優異的耐熱性和機械特性(屈服強度和屈服點)的聚醯亞胺膜及其製造方法。Therefore, an object of the present invention is to provide a polyimide film having excellent heat resistance and mechanical properties (yield strength and yield point) and a method for producing the same.
但是,本發明要解決的課題不限於以上提及的課題,未提及的其他課題是從業人員可以從以下記載明確理解的。 [技術方案] However, the issues to be solved by the present invention are not limited to the issues mentioned above, and other issues not mentioned can be clearly understood by practitioners from the following description. [Technical Solution]
為了達成如上所述目的,本發明一個態樣提供一種可撓性覆金屬箔層壓板,其屈服強度為138 MPa以上,玻璃轉化溫度(glass transition temperature)為370℃以上。In order to achieve the above-mentioned object, one aspect of the present invention provides a flexible metal-clad laminate having a yield strength of 138 MPa or more and a glass transition temperature of 370°C or more.
本發明另一態樣提供一種包括前述聚醯亞胺膜和導電性金屬箔的可撓性覆金屬箔層壓板。Another aspect of the present invention provides a flexible metal-clad laminate comprising the aforementioned polyimide film and a conductive metal foil.
本發明又一態樣提供一種包括前述可撓性覆金屬箔層壓板的電子部件。 [發明效果] Another aspect of the present invention provides an electronic component including the aforementioned flexible metal-clad foil laminate. [Effect of the invention]
本發明藉由提供調節了二酐和二胺成分的配比、反應比等的聚醯亞胺膜,從而提供具有優異的耐熱性、屈服點和屈服強度特性的聚醯亞胺膜,從而可以改善聚醯亞胺膜的加工性能。The present invention provides a polyimide film having excellent heat resistance, yield point and yield strength characteristics by providing a polyimide film in which the ratio and reaction ratio of dianhydride and diamine components are adjusted, thereby improving the processing performance of the polyimide film.
這種聚醯亞胺膜可以應用於要求特性優異的聚醯亞胺膜的多樣領域,例如,可以應用於根據金屬化法製造的可撓性覆金屬箔層壓板或包括這種可撓性覆金屬箔層壓板的電子部件。This polyimide film can be applied to various fields requiring a polyimide film with excellent characteristics, for example, it can be applied to a flexible metal-clad laminated plate manufactured according to a metallization method or an electronic component including this flexible metal-clad laminated plate.
本說明書和申請專利範圍中使用的術語或詞語不得限定為通常的或詞典的意義進行解釋,應立足於「發明人為了以最佳方法說明其自身的發明而可以適當地定義術語的概念」的原則,只解釋為符合本發明的技術思想的意義和概念。The terms or words used in this specification and the scope of the patent application shall not be interpreted in a limited manner to the usual or dictionary meanings, but shall be based on the principle that "the inventor can appropriately define the concept of the term in order to explain his own invention in the best way" and shall only be interpreted as the meaning and concept that conforms to the technical idea of the present invention.
因此,本說明書中記載的實施例的構成只不過是本發明最佳的一個實施例,並不全部代表本發明的技術思想,因此應理解為在本申請時間點會存在可以替代其多樣均等物和變形例。Therefore, the embodiments described in this specification are merely the best embodiments of the present invention and do not fully represent the technical ideas of the present invention. Therefore, it should be understood that there will be various equivalents and modifications that can replace them at the time of this application.
只要上下文未明確表示不同,本說明書中單數的表達包括複數的表達。在本說明書中,「包括」「具備」或「具有」等術語是要指定實施的特徵、數字、步驟、構成要素或其組合的存在,應理解為不預先排除一個或其以上的其他特徵或數字、步驟、構成要素或其組合的存在或附加可能性。Unless the context clearly indicates otherwise, singular expressions in this specification include plural expressions. In this specification, terms such as "including", "having" or "having" are intended to specify the existence of features, numbers, steps, constituent elements or combinations thereof of the implementation, and should be understood as not excluding the existence or additional possibility of one or more other features or numbers, steps, constituent elements or combinations thereof in advance.
在本說明書中,「二酐」意指包括其前驅物或衍生物,其在技術上可能不是二酐,但儘管如此,與二胺反應而形成聚醯胺酸,該聚醯胺酸可以再次變換成聚醯亞胺。In this specification, "dianhydride" is meant to include precursors or derivatives thereof which may not technically be dianhydrides but nevertheless react with diamines to form polyamides which can in turn be converted into polyimines.
在本說明書中,「二胺」意指包括其前驅物或衍生物,其在技術上可能不是二胺,但儘管如此,與二酐反應而形成聚醯胺酸,該聚醯胺酸可以再次變換成聚醯亞胺。In this specification, "diamine" is meant to include precursors or derivatives thereof which may not technically be diamines but nevertheless react with dianhydrides to form polyamides which can in turn be converted into polyimines.
在本說明書中,當藉由列舉範圍、較佳範圍或較佳上限值和較佳下限值而給出量、濃度或其他值或參數時,無論範圍是否另行公開,應理解為具體公開了由任意一對的任意範圍上限值或較佳值和任意範圍下限值或較佳值形成的所有範圍。In this specification, 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 by 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 separately.
數值的範圍在本說明書中提及時,只要未不同地敘述,其範圍意指包括其終點及其範圍內的所有整數和分數。本發明的範疇意指不限定為在定義範圍時提及的特定值。When a range of numerical values is mentioned in this specification, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within the range. The scope of the present invention is not intended to be limited to the specific values mentioned when defining the range.
在本說明書中表示數值範圍的「a至b」和「a~b」中,「至」和「~」定義為≥a且≤b。In this specification, in "a to b" and "a~b" indicating a numerical range, "to" and "~" are defined as ≥a and ≤b.
本發明一實現例的聚醯亞胺膜,屈服強度可以為138 MPa以上,玻璃轉化溫度可以為370℃以上。The polyimide film of an embodiment of the present invention may have a yield strength of 138 MPa or more and a glass transition temperature of 370° C. or more.
另一方面,前述聚醯亞胺膜的屈服強度可以為150 MPa以下,玻璃轉化溫度可以為380℃以下。On the other hand, the polyimide film may have a yield strength of 150 MPa or less and a glass transition temperature of 380° C. or less.
例如,前述聚醯亞胺膜的屈服強度可以為138 MPa以上、140 MPa以上、145 MPa以上。For example, the yield strength of the polyimide film may be 138 MPa or more, 140 MPa or more, or 145 MPa or more.
在一實現例中,前述聚醯亞胺膜的屈服點可以為2.4%以上。In one implementation example, the yield point of the polyimide film may be greater than 2.4%.
另一方面,前述聚醯亞胺膜的屈服點可以為2.6%以下。On the other hand, the yield point of the polyimide film may be 2.6% or less.
在一實現例中,前述聚醯亞胺膜可以藉由使包含二酐成分和二胺成分的聚醯胺酸溶液發生醯亞胺化反應而獲得,其中,前述二酐成分包括聯苯四甲酸二酐(BPDA)、均苯四甲酸二酐(PMDA)和二苯酮四羧酸二酐(BTDA),前述二胺成分包括對苯二胺(PPD)、間聯甲苯胺(m-tolidine)和二胺基二苯醚(ODA)。In one embodiment, the polyimide film can be obtained by subjecting a polyimide solution containing a dianhydride component and a diamine component to an imidization reaction, wherein the dianhydride component includes biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA) and benzophenonetetracarboxylic dianhydride (BTDA), and the diamine component includes p-phenylenediamine (PPD), m-tolidine and diaminodiphenyl ether (ODA).
即,前述聚醯亞胺膜可以使源自由聯苯四甲酸二酐、均苯四甲酸二酐、二苯酮四羧酸二酐、對苯二胺、間聯甲苯胺和二胺基二苯醚構成的聚合物的聚醯胺酸發生醯亞胺化而獲得。That is, the polyimide film can be obtained by imidizing a polyamide derived from a polymer composed of biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, p-phenylenediamine, m-tolidine and diaminodiphenyl ether.
在一實現例中,以前述二酐成分的總含量100莫耳%為基準,前述聯苯四甲酸二酐的含量可以為15莫耳%以上、30莫耳%以下,前述均苯四甲酸二酐的含量可以為30莫耳%以上、50莫耳%以下,前述二苯酮四羧酸二酐的含量可以為25莫耳%以上、45莫耳%以下。In one implementation example, based on the total content of the aforementioned dianhydride components being 100 mol %, the content of the aforementioned biphenyltetracarboxylic dianhydride may be greater than 15 mol % and less than 30 mol %, the content of the aforementioned pyromellitic dianhydride may be greater than 30 mol % and less than 50 mol %, and the content of the aforementioned benzophenone tetracarboxylic dianhydride may be greater than 25 mol % and less than 45 mol %.
例如,以前述二酐成分的總含量100莫耳%為基準,前述聯苯四甲酸二酐的含量可以為20莫耳%以上、25莫耳%以下,前述均苯四甲酸二酐的含量可以為35莫耳%以上、45莫耳%以下,前述二苯酮四羧酸二酐的含量可以為30莫耳%以上、45莫耳%以下。For example, based on 100 mol % of the total content of the dianhydride components, the content of the biphenyltetracarboxylic dianhydride may be greater than 20 mol % and less than 25 mol %, the content of the pyromellitic dianhydride may be greater than 35 mol % and less than 45 mol %, and the content of the benzophenone tetracarboxylic dianhydride may be greater than 30 mol % and less than 45 mol %.
在一實現例中,以前述二胺成分的總含量100莫耳%為基準,前述對苯二胺的含量可以為45莫耳%以上、60莫耳%以下,前述間聯甲苯胺的含量可以為10莫耳%以上、25莫耳%以下,前述二胺基二苯醚的含量可以為20莫耳%以上、40莫耳%以下。In one embodiment, based on the total content of the aforementioned diamine components being 100 mol %, the content of the aforementioned p-phenylenediamine may be greater than 45 mol % and less than 60 mol %, the content of the aforementioned m-tolidine may be greater than 10 mol % and less than 25 mol %, and the content of the aforementioned diaminodiphenyl ether may be greater than 20 mol % and less than 40 mol %.
例如,以前述二胺成分的總含量100莫耳%為基準,前述對苯二胺的含量可以為50莫耳%以上、60莫耳%以下,前述間聯甲苯胺的含量可以為10莫耳%以上、15莫耳%以下,前述二胺基二苯醚的含量可以為25莫耳%以上、35莫耳%以下。For example, based on 100 mol % of the total content of the aforementioned diamine components, the content of the aforementioned p-phenylenediamine can be greater than 50 mol % and less than 60 mol %, the content of the aforementioned m-tolidine can be greater than 10 mol % and less than 15 mol %, and the content of the aforementioned diaminodiphenyl ether can be greater than 25 mol % and less than 35 mol %.
本發明的對苯二胺為剛性單體,隨著對苯二胺含量的增加,合成的聚醯亞胺具有更加線性的結構,有助於提高聚醯亞胺的機械特性和耐熱性。The p-phenylenediamine of the present invention is a rigid monomer. With the increase of the p-phenylenediamine content, the synthesized polyimide has a more linear structure, which helps to improve the mechanical properties and heat resistance of the polyimide.
另外,間聯甲苯胺尤其包含具有甲基的苯環結構,可以有助於提高聚醯亞胺膜的機械特性和耐熱性。In addition, meta-tolidine particularly contains a benzene ring structure having a methyl group, which can contribute to improving the mechanical properties and heat resistance of the polyimide film.
本發明的來源於聯苯四甲酸二酐的聚醯亞胺鏈具有被命名為電荷轉移複合物(CTC:Charge transfer complex)的結構,即,電子供體(electron donnor)與電子受體(electron acceptor)彼此接近配置的規則性直線結構,加強了分子間相互作用(intermolecular interaction),影響聚醯亞胺膜的耐熱性和機械特性。The polyimide chain derived from biphenyltetracarboxylic dianhydride of the present invention has a structure named as a charge transfer complex (CTC), that is, a regular linear structure in which electron donors and electron acceptors are arranged close to each other, which strengthens the intermolecular interaction and affects the heat resistance and mechanical properties of the polyimide film.
另外,均苯四甲酸二酐是具有相對剛性結構的二酐成分,能夠賦予聚醯亞胺膜適當的彈性。In addition, pyromellitic dianhydride is a dianhydride component with a relatively rigid structure and can impart appropriate elasticity to the polyimide film.
聚醯亞胺膜為了具有優異的機械特性和耐熱性,二酐的含量比很重要。例如,聯苯四甲酸二酐的含量比越少,因前述CTC結構導致的機械特性和耐熱性也會越低下。In order for polyimide film to have excellent mechanical properties and heat resistance, the content ratio of dianhydride is very important. For example, the lower the content ratio of biphenyltetracarboxylic dianhydride, the lower the mechanical properties and heat resistance caused by the aforementioned CTC structure.
另外,聯苯四甲酸二酐及二苯酮四羧酸二酐包含與芳族部分相應的2個苯環,相反,均苯四甲酸二酐包含與芳族部分相應的1個苯環。In addition, biphenyltetracarboxylic dianhydride and benzophenonetetracarboxylic dianhydride contain two benzene rings corresponding to the aromatic part, whereas pyromellitic dianhydride contains one benzene ring corresponding to the aromatic part.
在二酐成分中,均苯四甲酸二酐含量的增加,在以相同分子量為基準時,可以理解為分子內的醯亞胺基增加,這可以理解為在聚醯亞胺高分子鏈上,來源於前述均苯四甲酸二酐的醯亞胺基的比率比來源於聯苯四甲酸二酐和二苯酮四羧酸二酐的醯亞胺基相對增加。In the dianhydride component, the increase in the content of pyromellitic dianhydride can be understood as an increase in the imide groups in the molecule when the molecular weight is the same. This can be understood as the ratio of the imide groups derived from the aforementioned pyromellitic dianhydride to the imide groups derived from biphenyltetracarboxylic dianhydride and dibenzophenonetetracarboxylic dianhydride in the polyimide polymer chain is relatively increased.
即,均苯四甲酸二酐含量的過度增加,即使相對於全體聚醯亞胺膜,也可以視為醯亞胺基的相對增加,因此難以期待提高機械特性和耐熱性。That is, an excessive increase in the content of pyromellitic dianhydride can be regarded as a relative increase in imide groups even with respect to the entire polyimide film, so it is difficult to expect improvements in mechanical properties and heat resistance.
相反,若均苯四甲酸二酐的含量比過度減少,則剛性結構的成分相對減少,聚醯亞胺膜的彈性會下降到希望的水平以下。On the contrary, if the content of pyromellitic dianhydride is excessively reduced, the rigid structural component is relatively reduced and the elasticity of the polyimide film will drop below the desired level.
由於這種理由,前述聯苯四甲酸二酐的含量超過前述範圍或均苯四甲酸二酐的含量低於前述範圍時,聚醯亞胺膜的機械特性和耐熱性會低下。For this reason, when the content of the biphenyltetracarboxylic dianhydride exceeds the above range or the content of the pyromellitic dianhydride is below the above range, the mechanical properties and heat resistance of the polyimide film are reduced.
相反,前述聯苯四甲酸二酐的含量低於前述範圍或均苯四甲酸二酐的含量超過前述範圍時,也會對聚醯亞胺膜的機械特徵和耐熱性產生不良影響。On the contrary, when the content of the biphenyltetracarboxylic dianhydride is lower than the above range or the content of the pyromellitic dianhydride exceeds the above range, it will also have an adverse effect on the mechanical properties and heat resistance of the polyimide film.
因此,本案的聚醯亞胺膜的作為二酐成分的聯苯四甲酸二酐、均苯四甲酸二酐和二苯酮四羧酸二酐各個的含量範圍和作為二胺成分的對苯二胺、間聯甲苯胺和二胺基二苯醚各個的含量範圍若高於或低於本案的含量範圍,則耐熱性(玻璃轉化溫度)和/或機械特性(屈服點、屈服強度)會低下。Therefore, if the content ranges of biphenyltetracarboxylic dianhydride, isomellitic dianhydride and dibenzophenone tetracarboxylic dianhydride as dianhydride components and the content ranges of p-phenylenediamine, m-toluidine and diaminodiphenyl ether as diamine components of the polyimide film of the present case are higher or lower than the content ranges of the present case, the heat resistance (glass transition temperature) and/or mechanical properties (yield point, yield strength) will be reduced.
在一實現例中,前述聚醯亞胺膜的前述聚醯亞胺可以為包含第一嵌段的嵌段共聚物,前述第一嵌段是使包括前述聯苯四甲酸二酐的二酐成分與包括前述間聯甲苯胺的二胺成分發生醯亞胺化反應而獲得。In one implementation example, the polyimide of the polyimide film may be a block copolymer including a first block, wherein the first block is obtained by subjecting a dianhydride component including the biphenyltetracarboxylic dianhydride to an imidization reaction with a diamine component including the meta-tolidine.
即,前述聚醯亞胺可以為包含2個以上嵌段的嵌段共聚物。That is, the polyimide may be a block copolymer including two or more blocks.
另一方面,前述第一嵌段可以使源於由聯苯四甲酸二酐構成的二酐成分和由間聯甲苯胺構成的二胺成分的聚合物的聚醯胺酸發生醯亞胺化而獲得。On the other hand, the first block can be obtained by imidizing a polyamide derived from a polymer of a dianhydride component consisting of biphenyltetracarboxylic dianhydride and a diamine component consisting of m-tolidine.
在一實現例中,以前述聚醯亞胺的總含量100莫耳%為基準,前述第一嵌段的含量可以為10莫耳%以上、16莫耳%以下。In one implementation example, based on 100 mol % of the total content of the polyimide, the content of the first block may be greater than 10 mol % and less than 16 mol %.
若前述第一嵌段的含量低於本案範圍,則聚醯亞胺膜的玻璃轉化溫度降低,耐熱性會低下。另外,若前述第一嵌段的含量超過本案的範圍,則聚醯亞胺膜的屈服點和/或屈服強度會低下。If the content of the first block is lower than the range of the present invention, the glass transition temperature of the polyimide film is lowered and the heat resistance is reduced. In addition, if the content of the first block exceeds the range of the present invention, the yield point and/or yield strength of the polyimide film is reduced.
在本發明中,聚醯胺酸的製造例如可以有以下方法等: (1)方法,將二胺成分全量加入溶劑中,然後添加二酐成分使得與二胺成分實質上達到等莫耳並進行聚合; (2)方法,將二酐成分全量加入溶劑中,然後添加二胺成分使得與二酐成分實質上達到等莫耳並進行聚合; (3)方法,將二胺成分中一部分成分加入溶劑中後,相對於反應成分,將二酐成分中一部分成分按約95~105莫耳%的比率混合後,添加剩餘二胺成分,接著添加剩餘二酐成分,使二胺成分和二酐成分實質上達到等莫耳並進行聚合; (4)方法,將二酐成分加入溶劑中後,相對於反應成分,將二胺化合物中一部分成分按95~105莫耳%比率混合後,添加其他二酐成分,接著添加剩餘二胺成分,使二胺成分和二酐成分實質上達到等莫耳並進行聚合; (5)方法,在溶劑中使一部分二胺成分與一部分二酐成分反應以便使得某一者過量,形成第一組合物,在又一溶劑中,使一部分二胺成分與一部分二酐成分反應以便使得某一者過量,形成第二組合物後,混合第一、第二組合物並完成聚合,此時,在形成第一組合物時,若二胺成分過剩,則在第二組合物中使二酐成分過量,在第一組合物中二酐成分過剩時,則在第二組合物中使二胺成分過量,混合第一、第二組合物以使得這些反應所使用的全體二胺成分和二酐成分實質上達到等莫耳,並進行聚合。 In the present invention, the production of polyamine acid can be carried out by the following methods, for example: (1) A method of adding the entire amount of the diamine component to a solvent, and then adding the dianhydride component so that the diamine component and the dianhydride component are substantially equimolar and polymerizing; (2) A method of adding the entire amount of the dianhydride component to a solvent, and then adding the diamine component so that the diamine component and the dianhydride component are substantially equimolar and polymerizing; (3) A method of adding a portion of the diamine component to a solvent, mixing a portion of the dianhydride component at a ratio of about 95 to 105 mol% relative to the reaction component, adding the remaining diamine component, and then adding the remaining dianhydride component so that the diamine component and the dianhydride component are substantially equimolar and polymerizing; (4) Method, after adding the dianhydride component to the solvent, relative to the reaction component, a portion of the diamine compound is mixed at a ratio of 95-105 mol%, and then the other dianhydride components are added, and then the remaining diamine components are added, so that the diamine component and the dianhydride component are substantially equal in molar ratio and then polymerized; (5) A method comprising reacting a portion of a diamine component with a portion of a dianhydride component in a solvent so that one of them is excessive to form a first composition, reacting a portion of a diamine component with a portion of a dianhydride component in another solvent so that one of them is excessive to form a second composition, mixing the first and second compositions and completing polymerization. At this time, if the diamine component is excessive when forming the first composition, the dianhydride component is excessive in the second composition, and if the dianhydride component is excessive in the first composition, the diamine component is excessive in the second composition. The first and second compositions are mixed so that the total diamine component and dianhydride component used in these reactions are substantially equimolar, and then polymerization is performed.
在本發明中,可以將如上所述的聚醯胺酸的聚合方法定義為任意(random)聚合方式,藉由如上所述過程製造的本發明的從聚醯胺酸製造的聚醯亞胺膜,在使本發明的效果達到最大方面可以較佳適用。In the present invention, the polymerization method of polyamic acid as described above can be defined as a random polymerization method, and the polyimide film produced from polyamic acid of the present invention produced by the above process can be preferably applied in maximizing the effect of the present invention.
不過,前述聚合方法由於前面描述的高分子鏈內的反復單位的長度製造得相對較短,因而在發揮來源於二酐成分的聚醯亞胺鏈具有的各種優異特性方面會存在局限。因此,本發明尤其可以較佳利用的聚醯胺酸的聚合方法可以為嵌段聚合方式。However, the aforementioned polymerization method has limitations in terms of exerting the various excellent properties of the polyimide chain derived from the dianhydride component because the length of the repeating unit in the polymer chain described above is relatively short. Therefore, the polymerization method of polyamide acid that can be particularly preferably utilized in the present invention can be a block polymerization method.
在一個具體示例中,本發明的聚醯亞胺膜的製造方法可以包括:In a specific example, the method for manufacturing the polyimide film of the present invention may include:
將聯苯四甲酸二酐和間聯甲苯胺在有機溶劑中聚合而製造包含嵌段共聚物的第一嵌段的聚醯胺酸的步驟。The invention further comprises a step of polymerizing biphenyltetracarboxylic dianhydride and meta-tolidine in an organic solvent to prepare a polyamide comprising a first block of a block copolymer.
另外,前述聚醯亞胺膜的製造方法可以包括:除形成前述第一嵌段的聯苯四甲酸二酐和間聯甲苯胺之外,組合其餘二酐成分和二胺成分,製造在第一嵌段之外包含體現聚醯亞胺膜特性所需的追加嵌段的聚醯胺酸的步驟。In addition, the method for producing the polyimide film may include: in addition to the biphenyltetracarboxylic dianhydride and meta-tolidine forming the first block, the remaining dianhydride components and diamine components are combined to produce a polyamide containing an additional block required to embody the characteristics of the polyimide film in addition to the first block.
另一方面,包含嵌段共聚物的第一嵌段的聚醯胺酸既可以先於包含其他嵌段的聚醯胺酸而製造,也可以在先製造了包括其他嵌段的聚醯胺酸後,再製造包含第一嵌段的聚醯胺酸。On the other hand, the polyamine comprising the first block of the block copolymer can be prepared before the polyamine comprising other blocks, or the polyamine comprising other blocks can be prepared first and then the polyamine comprising the first block.
例如,也可以在一同投入聯苯四甲酸二酐和間聯甲苯胺以製造包含第一嵌段的聚醯胺酸後,向包含所製造的第一嵌段的聚醯胺酸中,按既定順序進一步投入形成其餘嵌段的二酐成分和二胺成分並進行醯亞胺化以製造作為嵌段共聚物的聚醯亞胺。For example, after biphenyltetracarboxylic dianhydride and meta-tolidine are added together to produce a polyamide containing a first block, a dianhydride component and a diamine component that form the remaining blocks are further added to the polyamide containing the produced first block in a predetermined order and imidized to produce a polyimide as a block copolymer.
另外,還可以首先製造包含並非第一嵌段的嵌段的聚醯胺酸後,或在製造包含並非第一嵌段的嵌段的聚醯胺酸期間,在所製造的包含並非第一嵌段的嵌段的聚醯胺酸中一同投入聯苯四甲酸二酐和間聯甲苯胺以製造包含第一嵌段的聚醯胺酸。In addition, after first manufacturing a polyamide containing a block other than the first block, or during the manufacturing of the polyamide containing a block other than the first block, biphenyltetracarboxylic dianhydride and meta-tolidine can be added to the manufactured polyamide containing a block other than the first block to manufacture the polyamide containing the first block.
另一方面,用於合成聚醯胺酸的溶劑不特別限定,只要是使聚醯胺酸溶解的溶劑,則任何溶劑均可使用,但較佳為醯胺類溶劑。On the other hand, the solvent used for synthesizing polyamine is not particularly limited, and any solvent can be used as long as it can dissolve polyamine, but an amide solvent is preferred.
具體地,前述溶劑可以為有機極性溶劑,詳細地,可以為非質子極性溶劑(aprotic polar solvent),例如,可以為選自由N,N-二甲基甲醯胺(DMF)、N,N-二甲基乙醯胺、N-甲基吡咯啶酮(NMP)、γ-丁內酯(GBL)、二甘醇二甲醚(Diglyme)構成的組的一種以上,但不限定於此,可以根據需要而單獨使用或組合2種以上使用。Specifically, the aforementioned solvent may be an organic polar solvent, more specifically, an aprotic polar solvent, for example, one or more selected from the group consisting of N,N-dimethylformamide (DMF), N,N-dimethylacetamide, N-methylpyrrolidone (NMP), γ-butyrolactone (GBL), and diglyme (Diglyme), but is not limited thereto and may be used alone or in combination of two or more as needed.
在一個示例中,前述溶劑尤其可以較佳使用N,N-二甲基甲醯胺和N,N-二甲基乙醯胺。In one example, the aforementioned solvent may preferably include N,N-dimethylformamide and N,N-dimethylacetamide.
另外,在聚醯胺酸製造製程中,也可以添加填充材料以改善滑動性、導熱性、耐電暈性、環硬度等膜的多種特性。添加的填充材料不特別限定,作為較佳示例,可以例如二氧化矽、氧化鈦、氧化鋁、氮化矽、氮化硼、磷酸氫鈣、磷酸鈣、雲母等。In addition, during the polyamide manufacturing process, fillers may be added to improve various properties of the film, such as slip, thermal conductivity, corona resistance, and ring hardness. The added fillers are not particularly limited, and preferred examples include silicon dioxide, titanium oxide, aluminum oxide, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, and mica.
填充材料的粒徑不特別限定,可以根據需改質的薄膜特性和添加的填充材料種類來決定。一般而言,平均粒徑為0.05 μm至100 μm,較佳為0.1 μm至75 μm,更佳為0.1 μm至50 μm,尤其較佳為0.1 μm至25 μm。The particle size of the filler is not particularly limited and can be determined according to the film properties to be improved and the type of filler added. Generally speaking, the average particle size is 0.05 μm to 100 μm, preferably 0.1 μm to 75 μm, more preferably 0.1 μm to 50 μm, and particularly preferably 0.1 μm to 25 μm.
若粒徑低於該範圍,則難以表現出改質效果,若超過該範圍,則存在極大損傷表面性或機械特性大幅下降的情形。If the particle size is below this range, the modification effect is difficult to show, and if it exceeds this range, the surface properties may be greatly damaged or the mechanical properties may be greatly reduced.
另外,對於填充材料的添加量也不特別限定,可以根據需改質的薄膜特性或填充材料粒徑等決定。一般而言,填充材料的添加量相對於聚醯亞胺100重量份,為0.01至100重量份,較佳為0.01至90重量份,更佳為0.02至80重量份。In addition, the amount of filler added is not particularly limited and can be determined according to the film properties to be improved or the filler particle size, etc. Generally speaking, the amount of filler added is 0.01 to 100 parts by weight, preferably 0.01 to 90 parts by weight, and more preferably 0.02 to 80 parts by weight, relative to 100 parts by weight of polyimide.
若填充材料添加量低於該範圍,則難以表現出填充材料的改質效果,若超過該範圍,則存在薄膜機械特性受到極大損傷的可能性。填充材料的添加方法不特別限定,也可以使用公知的任何方法。If the amount of filler added is below this range, the improvement effect of the filler is difficult to show, and if it exceeds this range, there is a possibility that the mechanical properties of the film will be greatly damaged. The method of adding the filler is not particularly limited, and any known method can be used.
在本發明的製造方法中,聚醯亞胺膜可以根據熱醯亞胺化法和化學醯亞胺化法製造。In the manufacturing method of the present invention, the polyimide film can be manufactured according to the thermal imidization method and the chemical imidization method.
另外,也可以藉由熱醯亞胺化法和化學醯亞胺化法並用的複合醯亞胺化法製造。Alternatively, it can be produced by a combined imidization method using a thermal imidization method and a chemical imidization method.
所謂前述熱醯亞胺化法,是不使用化學催化劑而利用熱風或紅外線乾燥器等熱源來誘導醯亞胺化反應的方法。The so-called thermal imidization method is a method that uses a heat source such as hot air or an infrared dryer to induce the imidization reaction without using a chemical catalyst.
前述熱醯亞胺化法可以將前述凝膠膜在100至600℃範圍的可變溫度下進行熱處理,使凝膠膜中存在的醯胺基實現醯亞胺化,詳細地,可以在200至500℃下,更詳細地,可以在300至500℃下進行熱處理,使凝膠膜中存在的醯胺基實現醯亞胺化。The aforementioned thermal imidization method can heat-treat the aforementioned gel film at a variable temperature in the range of 100 to 600°C to imidize the amide groups present in the gel film. Specifically, the heat treatment can be performed at 200 to 500°C, and more specifically, at 300 to 500°C to imidize the amide groups present in the gel film.
不過,在形成凝膠膜的過程中,醯胺酸中一部分(約0.1莫耳%至10莫耳%)會被醯亞胺化,為此,可以在50℃至200℃範圍的可變溫度下乾燥聚醯胺酸組合物,這也可以包括於前述熱醯亞胺化法的範疇。However, during the process of forming the gel film, a portion of the polyamine (about 0.1 mol% to 10 mol%) will be imidized. For this purpose, the polyamine composition can be dried at a variable temperature in the range of 50°C to 200°C, which can also be included in the scope of the aforementioned thermal imidization method.
就化學醯亞胺化法而言,可以根據本行業公知的方法,利用脫水劑和醯亞胺化劑來製造聚醯亞胺膜。In the chemical imidization method, a polyimide membrane can be produced using a dehydrating agent and an imidizing agent according to a method known in the industry.
作為複合醯亞胺化法的一個示例,可以在聚醯胺酸溶液中投入脫水劑和醯亞胺化劑後,在80至200℃下,較佳在100至180℃下加熱,在部分固化及乾燥後,在200至400℃下加熱5至400秒,從而可以製造聚醯亞胺膜。As an example of the composite imidization method, a dehydrating agent and an imidizing agent may be added to a polyamide solution, and then heated at 80 to 200°C, preferably 100 to 180°C. After partial curing and drying, the solution may be heated at 200 to 400°C for 5 to 400 seconds to produce a polyimide film.
本發明提供包括上述聚醯亞胺膜的多層膜。The present invention provides a multilayer film including the above-mentioned polyimide film.
前述多層膜可以包括熱可塑性聚醯亞胺膜等補充的聚醯亞胺膜。The aforementioned multi-layer film may include a supplementary polyimide film such as a thermoplastic polyimide film.
本發明提供一種包括上述聚醯亞胺膜和導電性金屬箔的可撓性覆金屬箔層壓板。The present invention provides a flexible metal-clad laminate comprising the polyimide film and a conductive metal foil.
作為使用的金屬箔,不特別限定,但在將本發明的可撓性金屬箔層壓板用於電子部件或電子設備用途的情況下,例如可以為包括銅或銅合金、不鏽鋼或其合金、鎳或鎳合金(也包括42合金)、鋁或鋁合金的金屬箔。The metal foil used is not particularly limited, but when the flexible metal foil laminate of the present invention is used for electronic components or electronic equipment, for example, it can be a metal foil including copper or copper alloys, stainless steel or its alloys, nickel or nickel alloys (including 42 alloys), aluminum or aluminum alloys.
在普通的可撓性金屬箔層壓板中,廣泛使用被稱為軋製銅箔、電解銅箔的銅箔,在本發明中也可以較佳使用。另外,在這些金屬箔表面也可以被覆防鏽層、耐熱層或黏合層。In common flexible metal foil laminated plates, copper foils called rolled copper foils and electrolytic copper foils are widely used, and can also be preferably used in the present invention. In addition, the surfaces of these metal foils can also be coated with a rust-proof layer, a heat-resistant layer or an adhesive layer.
在本發明中,對於前述金屬箔的厚度不特別限定,只要是能夠根據其用途充分發揮功能的厚度即可。In the present invention, the thickness of the metal foil is not particularly limited as long as it is a thickness that can fully exert its function according to its application.
本發明的可撓性覆金屬箔層壓板可以是在前述聚醯亞胺膜的至少一面層疊了金屬箔的結構。The flexible metal foil-clad laminated plate of the present invention may be a structure in which a metal foil is laminated on at least one side of the polyimide film.
下文藉由發明的具體製造例和實施例,更詳細描述發明的作用和效果。不過,這種製造例和實施例只是作為發明示例而提出的,發明的權利範圍不由此限定。 [ 製造例:聚醯亞胺膜的製造 ] The following is a more detailed description of the functions and effects of the invention through specific manufacturing examples and embodiments of the invention. However, such manufacturing examples and embodiments are only provided as examples of the invention, and the scope of the invention is not limited thereby. [ Manufacturing Example: Manufacturing of Polyimide Film ]
本發明的聚醯亞胺膜可以藉由如下本行業公知的通常方法製造。首先,使前述二酐與二胺成分在有機溶劑中反應而獲得聚醯胺酸溶液。The polyimide film of the present invention can be produced by the following common method known in the industry: First, the dianhydride and the diamine component are reacted in an organic solvent to obtain a polyimide solution.
此時,溶劑一般為醯胺類溶劑,可以使用非質子極性溶劑(Aprotic solvent),例如可以使用N,N'-二甲基甲醯胺、N,N'-二甲基乙醯胺、N-甲基吡咯啶酮或其組合。At this time, the solvent is generally an amide solvent, and an aprotic polar solvent (Aprotic solvent) can be used, for example, N,N'-dimethylformamide, N,N'-dimethylacetamide, N-methylpyrrolidone or a combination thereof can be used.
前述二酐與二胺成分的投入形態可以以粉末、團塊和溶液形態投入,在反應初期以粉末形態投入而進行反應後,為了調節聚合黏度,較佳以溶液形態投入。The dianhydride and diamine components can be added in the form of powder, agglomerate or solution. In the initial stage of the reaction, they are added in the form of powder. After the reaction, in order to adjust the polymerization viscosity, they are preferably added in the form of solution.
獲得的聚醯胺酸溶液可以與醯亞胺化催化劑和脫水劑混合,並塗覆於支撐體。The obtained polyamine solution can be mixed with an imidization catalyst and a dehydrating agent and coated on a support.
作為使用的催化劑的示例,有叔胺類( 例如,異喹啉、β-甲基吡啶、吡啶等),作為脫水劑的示例,有酸酐,但不限於此。另外,作為上述使用的支撐體,可以例如玻璃板、鋁箔、循環不鏽鋼帶或不鏽鋼桶等,但不限於此。Examples of the catalyst used include tertiary amines (e.g., isoquinoline, β-picoline, pyridine, etc.), and examples of the dehydrating agent include acid anhydrides, but are not limited to these. In addition, the support used above may include, for example, a glass plate, an aluminum foil, a circulating stainless steel belt, or a stainless steel drum, but are not limited to these.
在前述支撐體上塗覆的薄膜藉由乾燥空氣和熱處理而在支撐體上凝膠化。The film coated on the aforementioned support is gelled on the support by dry air and heat treatment.
前述凝膠化的薄膜從支撐體分離並進行熱處理,以實現乾燥和醯亞胺化。The gelled film is separated from the support and heat treated to achieve drying and imidization.
完成前述熱處理的薄膜可以在既定張力下進行熱處理,以去除在製膜過程中發生的薄膜內部殘留應力。The film that has completed the above heat treatment can be heat treated under a predetermined tension to remove the residual stress inside the film that occurs during the film forming process.
具體地,在向具備攪拌器和氮氣注入/排出管的反應器中注入氮氣的同時投入500ml的DMF,將反應器的溫度設置為25℃後,將聯苯四甲酸二酐(BPDA)、均苯四甲酸二酐(PMDA)、二苯酮四羧酸二酐(BTDA)、對苯二胺(PPD)、間聯甲苯胺(m-tolidine)、二胺基二苯醚(ODA)和4,4'-二胺基苯甲醯苯胺(4,4'-二胺基苯甲醯苯胺)按照調節的組分和確定的順序投入並使其完全溶解。Specifically, 500 ml of DMF was added while nitrogen was injected into a reactor equipped with a stirrer and a nitrogen injection/exhaust pipe, and after the temperature of the reactor was set to 25°C, biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), benzophenonetetracarboxylic dianhydride (BTDA), p-phenylenediamine (PPD), m-tolidine, diaminodiphenyl ether (ODA) and 4,4'-diaminobenzanilide (4,4'-diaminobenzanilide) were added in the adjusted composition and determined order and completely dissolved.
投入時,可以連續投入聯苯四甲酸二酐和間聯甲苯胺,使包含聯苯四甲酸二酐的二酐成分與包含間聯甲苯胺的二胺成分發生醯亞胺化反應而獲得第一嵌段。During the addition, biphenyltetracarboxylic dianhydride and m-tolidine may be added continuously to allow the dianhydride component containing biphenyltetracarboxylic dianhydride and the diamine component containing m-tolidine to undergo an imidization reaction to obtain the first block.
然後,在氮氣氣氛下,使反應器的溫度升高到30℃並加熱的同時持續攪拌120分鐘,製造了一次反應黏度為800~1,200cP的聚醯胺酸。Then, under a nitrogen atmosphere, the temperature of the reactor was raised to 30°C and stirred for 120 minutes while heating, producing polyamine with a primary reaction viscosity of 800~1,200 cP.
攪拌如此製造的聚醯胺酸以便最終使黏度達到40,000~160,000cP。The polyamide thus produced is stirred so as to finally reach a viscosity of 40,000~160,000 cP.
調節催化劑和脫水劑含量並添加到所準備的最終聚醯胺酸中後,利用塗覆器製造了聚醯亞胺膜。 [ 實施例和比較 例 ] After adjusting the content of the catalyst and the dehydrating agent and adding them to the prepared final polyimide, a polyimide film was manufactured using a coater. [ Example and Comparative Example ]
如下表1所示,調節實施例1至實施例4和比較例1至比較例5中的二酐成分和前述二胺成分的含量,根據製造例製造了聚醯亞胺膜。As shown in Table 1 below, the contents of the dianhydride component and the aforementioned diamine component in Examples 1 to 4 and Comparative Examples 1 to 5 were adjusted, and polyimide films were manufactured according to the manufacturing examples.
另外,調節二酐成分和前述二胺成分的投入順序和投入量,實施例1至4和比較例1至3的聚醯亞胺膜雖然包括使包含聯苯四甲酸二酐的二酐成分和包含間聯甲苯胺的二胺成分發生醯亞胺化反應而獲得的第一嵌段,但比較例4和5的聚醯亞胺膜不包含使包含聯苯四甲酸二酐的二酐成分和包含間聯甲苯胺的二胺成分發生醯亞胺化反應而獲得的第一嵌段。In addition, by adjusting the order and amount of the dianhydride component and the aforementioned diamine component, although the polyimide films of Examples 1 to 4 and Comparative Examples 1 to 3 include the first block obtained by the imidization reaction of the dianhydride component containing biphenyltetracarboxylic acid dianhydride and the diamine component containing meta-tolidine, the polyimide films of Comparative Examples 4 and 5 do not include the first block obtained by the imidization reaction of the dianhydride component containing biphenyltetracarboxylic acid dianhydride and the diamine component containing meta-tolidine.
另外,比較例1至3的聚醯亞胺膜的使包含聯苯四甲酸二酐的二酐成分和包含間聯甲苯胺的二胺成分發生醯亞胺反應而獲得的第一嵌段的含量,以前述聚醯亞胺膜的總含量100莫耳%為基準,包含5莫耳%以上、8莫耳%以下。In addition, the content of the first block obtained by allowing the dianhydride component containing biphenyltetracarboxylic dianhydride and the diamine component containing meta-tolidine to undergo an amide reaction in the polyimide films of Comparative Examples 1 to 3 is greater than 5 mol% and less than 8 mol%, based on the total content of the aforementioned polyimide film of 100 mol%.
另一方面,實施例1至4的聚醯亞胺膜的使包含聯苯四甲酸二酐的二酐成分和包含間聯甲苯胺的二胺成分發生醯亞胺化反應而獲得的第一嵌段的含量,以前述聚醯亞胺膜的總含量100莫耳%為基準,均包含10莫耳%以上、16莫耳%以下。
[表1]
測量所製造的聚醯亞胺膜的玻璃轉化溫度(Tg)、屈服點和屈服強度並示於下表2中。
[表2]
上表2的玻璃轉化溫度(T g)利用DMA求出各薄膜的損耗彈性率和儲存彈性率,在其切線圖中,將拐點測量為了玻璃轉化溫度。 (2) 屈服點的屈服強度的測量 The glass transition temperature (T g ) in Table 2 above was used to determine the loss modulus and storage modulus of each film using DMA, and the inflection point in the tangent graph was measured as the glass transition temperature. (2) Measurement of yield strength at yield point
上表2的屈服點和屈服強度是將聚醯亞胺膜裁剪成15 mm×50 mm以製造試片,根據ASTM D 882基準,將拉伸速度設為200 mm/分鐘,使用拉伸試驗機(Instron 5564, 英斯特朗公司),在室溫(room temp.)下進行了測量。The yield point and yield strength in Table 2 above were measured by cutting the polyimide film into 15 mm × 50 mm specimens and setting the tensile speed to 200 mm/min at room temperature using a tensile tester (Instron 5564, Instron Corporation) according to ASTM D 882.
測量結果,實施例1至4的聚醯亞胺膜的玻璃轉化溫度為370℃以上,屈服點為2.4%以上,屈服強度為138 MPa以上。The measurement results show that the polyimide films of Examples 1 to 4 have a glass transition temperature of 370° C. or higher, a yield point of 2.4% or higher, and a yield strength of 138 MPa or higher.
比較二胺成分的含量相同、二酐成分的含量不同的實施例1和2的聚醯亞胺膜,可以確認隨著BPDA的含量增加、BTDA的含量減少,聚醯亞胺膜的玻璃轉化溫度小幅上升,屈服點小幅下降,屈服強度小幅增加。By comparing the polyimide films of Examples 1 and 2 having the same content of diamine components and different contents of dianhydride components, it can be confirmed that as the content of BPDA increases and the content of BTDA decreases, the glass transition temperature of the polyimide film increases slightly, the yield point decreases slightly, and the yield strength increases slightly.
比較實施例1和實施例3的聚醯亞胺膜,可以確認隨著增加BPDA和ODA的含量、減少PPD和BTDA的含量,聚醯亞胺膜的屈服點和屈服強度小幅降低。By comparing the polyimide films of Example 1 and Example 3, it can be confirmed that the yield point and yield strength of the polyimide film are slightly reduced as the content of BPDA and ODA increases and the content of PPD and BTDA decreases.
另外,比較二酐成分的含量相同、二胺成分的含量不同的實施例1和4,可以確認隨著ODA的含量增加、PPD和間聯甲苯胺的含量減少,玻璃轉化溫度小幅上升,屈服點小幅下降,屈服強度小幅增加。In addition, by comparing Examples 1 and 4 in which the content of the dianhydride component is the same but the content of the diamine component is different, it can be confirmed that as the content of ODA increases and the contents of PPD and meta-tolidine decrease, the glass transition temperature increases slightly, the yield point decreases slightly, and the yield strength increases slightly.
另一方面,與實施例1的聚醯亞胺膜相比,增加ODA的含量而減少PPD和間聯甲苯胺的含量的比較例1,其聚醯亞胺膜的玻璃轉化溫度小於370℃,屈服強度也低下,小於138 MPa。On the other hand, compared with the polyimide film of Example 1, the glass transition temperature of the polyimide film of Comparative Example 1 in which the content of ODA was increased and the contents of PPD and m-tolidine were reduced was less than 370° C., and the yield strength was also low, less than 138 MPa.
另外,與實施例1的聚醯亞胺膜相比,增加ODA的含量而減少間聯甲苯胺的含量的比較例3,其聚醯亞胺膜的玻璃轉化溫度小於370℃。In addition, compared with the polyimide film of Example 1, the glass transition temperature of the polyimide film of Comparative Example 3 in which the content of ODA was increased and the content of m-tolidine was reduced was less than 370°C.
與比較例1的聚醯亞胺膜相比,進一步增加PMDA和ODA的含量而進一步減少BTDA和PPD的含量的比較例2,其聚醯亞胺膜的屈服點和屈服強度均提高,但玻璃轉化溫度依然小於370℃。Compared with the polyimide film of Comparative Example 1, the yield point and yield strength of the polyimide film of Comparative Example 2, in which the contents of PMDA and ODA are further increased and the contents of BTDA and PPD are further reduced, are improved, but the glass transition temperature is still less than 370°C.
比較例3的聚醯亞胺膜相比,比較例1的聚醯亞胺膜,玻璃轉化溫度、屈服點和屈服強度均提高,但玻璃轉化溫度依然小於370℃。Compared with the polyimide film of Comparative Example 3, the glass transition temperature, yield point and yield strength of the polyimide film of Comparative Example 1 are all improved, but the glass transition temperature is still less than 370°C.
包含4,4'-DABA且不包含使包含聯苯四甲酸二酐的二酐成分與包含間聯甲苯胺的二胺成分發生醯亞胺化反應而獲得的嵌段的比較例4和比較例5,其聚醯亞胺膜與具有相同二酐成分的組份的實施例1和實施例4的聚醯亞胺膜相比,玻璃轉化溫度(小於370℃)下降。Comparative Examples 4 and 5, which contain 4,4'-DABA and do not contain a block obtained by an imidization reaction of a dianhydride component containing biphenyltetracarboxylic dianhydride and a diamine component containing meta-tolidine, have polyimide films having a lower glass transition temperature (less than 370°C) than the polyimide films of Examples 1 and 4 having the same dianhydride component.
因此可以確認,在本案適宜範圍內製造的實施例1至4的聚醯亞胺膜,其耐熱性( 玻璃轉化溫度)和機械特性(屈服強度和屈服點)均優異,但超出本案適宜範圍時,耐熱性和機械特性難以並存。Therefore, it can be confirmed that the polyimide films of Examples 1 to 4 manufactured within the appropriate range of the present case have excellent heat resistance (glass transition temperature) and mechanical properties (yield strength and yield point), but when exceeding the appropriate range of the present case, it is difficult for heat resistance and mechanical properties to coexist.
即,可以確認,具有耐熱性和機械特性而可以適用於多樣應用領域的聚醯亞胺膜是在本案適宜範圍內製造的聚醯亞胺膜。That is, it can be confirmed that the polyimide film which has heat resistance and mechanical properties and can be applied to a variety of application fields is a polyimide film produced within the appropriate range of the present case.
本發明的聚醯亞胺膜及聚醯亞胺膜的製造方法的實施例只是使本發明所屬技術領域的一般技藝人士能夠容易地實施本發明的較佳實施例,不限定於前述實施例,因而本發明的權利範圍不由此限定。因此,本發明的真正的技術保護範圍應根據附帶的申請專利範圍的技術思想確定。另外,在不超出本發明技術思想的範圍內,可以實現多種置換、變形及變更,這是從業人員不言而喻的,可以由從業人員容易地變更的部分也包括於本發明的權利範圍,這是不言而喻的。The embodiments of the polyimide film and the method for producing the polyimide film of the present invention are only preferred embodiments that enable ordinary skilled persons in the technical field to which the present invention belongs to easily implement the present invention, and are not limited to the aforementioned embodiments, and thus the scope of the present invention is not limited thereby. Therefore, the true technical protection scope of the present invention should be determined according to the technical idea of the accompanying patent application scope. In addition, it is self-evident for practitioners that various substitutions, deformations and changes can be realized within the scope of the technical idea of the present invention, and it is self-evident for practitioners that the parts that can be easily changed by practitioners are also included in the scope of the present invention.
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