一种自增感光敏聚酰亚胺的制备及性能

本研究合成了一种新型的具有不对称结构的芳香二胺单体,即2,4,6-三甲基-3-胺基苯基-3′-胺基苯基甲酮(TMPDA),并与3,3′-4,4′-二苯甲酮四羧酸二酐(BTDA)经低温聚合和化学亚胺化合成了一种可溶性光敏聚酰亚胺。采用FTIR、UV、DSC、TGA等测试手段对树脂的结构与性能进行了表征和研究。该种聚酰亚胺具有自增感特性,并经过紫外光(365nm)曝光后可以得到较清晰的阴图型图像。     

光敏聚酰亚胺的研究与应用进展

光敏聚酰亚胺因其优良的综合性能,被广泛地应用于微电子领域的绝缘层和保护层等。本文综述了光敏聚酰亚胺(PSPI)的最新研究进展、发展概况,并且分别对负性光敏聚酰亚胺和正性光敏聚酰亚胺的结构、性能、合成方法以及相关材料的实际应用进行了系统的阐述。     

含噁唑环均苯型聚酰亚胺的制备和表征

为了提高聚酰亚胺材(PI)料的耐热性能,以2,6-二(对氨基苯)苯并[1,2-d;5,4-d]二噁唑为单体,采用两步法与均苯四甲酸二酐(PMDA)合成出了新型聚酰亚胺薄膜.采用红外光谱、热分析等手段对其结构与性能进行了表征.测定了聚酰亚胺的预聚体-聚酰胺酸(PAA)的特性黏度达到1.18dL/g,玻璃化温度343℃,在空气中热失重温度为626℃,表现出优异的热氧化稳定性.评价了聚酰亚胺在各种溶剂中的溶解性能,均不溶于常规的极性溶剂,甚至在浓硫酸中也不溶解.经红外光谱测定,聚酰胺酸基本转化成聚酰亚胺.     

一种三元共聚型聚酰亚胺的制备与表征

以3,3'-二甲基-4,4'-二氨基二苯甲烷、1,3-双(4-氨基苯氧基)苯(1,3-APB)与3,3',4,4'-二苯醚四羧酸二酐(ODPA)进行缩聚反应,制得一种新型的三元共缩聚型聚酰亚胺。将此聚合物与两种二元共缩聚型聚酰亚胺的性能进行对此,发现三元共聚型聚酰亚胺的溶解性能、力学性能和热性能皆较好,且使用范围扩大。     

含苯并噁唑结构共聚酰亚胺的合成及其性能

联苯四羧酸二酐(BPDA)与4,4′-二氨基二苯醚(ODA)及自制的2,6-二(对氨基苯)苯并[1,2-d;5,4-d']二噁唑(DAPBBO)在二甲基乙酰胺中共聚,然后进行铺膜和热酰亚胺化,得到了含有双苯并噁唑的共聚酰亚胺薄膜,对其结构、热性能、力学性能及光学性能进行了表征。结果表明:杂环单体的引入提高了聚酰亚胺的力学性能,增加了聚酰亚胺的玻璃化转变温度,并且使聚酰亚胺薄膜具有良好的紫外吸收能力。     

聚酰亚胺的改性及应用进展

介绍了聚酰亚胺的合成工艺路线和研究动向,重点介绍了可溶性聚酰亚胺和透明性聚酰亚胺.对聚酰亚胺在新领域中的应用进行了概述,尤其采用光敏聚酰亚胺应用于紫外光（UV）固化耐高温涂料体系的可行性进行了展望.     

可溶性聚酰亚胺树脂的合成及其薄膜制备

以含支链3,3′-二乙基-4,4′-二氨基二苯甲烷(M-OEA)为二胺单体,采用高温一步法与四种二酐进行聚合,合成了四种聚酰亚胺(PI)树脂,并制备了一系列聚酰亚胺薄膜。对聚酰亚胺树脂进行了溶解性测试,并通过傅里叶红外光谱、紫外-可见分光光度计、差示扫描量热仪、热重分析仪、静态热机械分析仪及电子万能材料试验机对PI薄膜的结构、光学性能、热性能和力学性能进行了表征。结果表明,该系列树脂溶解性优异,薄膜热稳定性良好,5%热失重温度(T_d⁵)均在390℃以上,玻璃化转变温度(T_g)均高于230℃,两种半脂环族PI薄膜的光学性能优异,紫外截止波长280 nm。     

一种新型结构聚酰亚胺的合成与表征

以2,3,3',4'-二苯醚四甲酸二酐(a-ODPA)和4,4′-二氨基二苯醚(ODA)为单体原料,在二甲基乙酰胺(DMAC)中聚合,通过化学亚胺化合成了一种新型聚酰亚胺,并在高温高压下模塑成型。通过热重分析(TGA)、差示扫描量热分析(DSC)和动态机械分析(DMA)等,对该聚酰亚胺的热性能进行了研究,并将其与以3,4,3',4'-二苯醚四甲酸二酐(s-ODPA)和ODA为单体原料合成的聚酰亚胺(牌号:YS20)进行比较。结果表明该聚酰亚胺具有良好的机械性能、热性能和加工性能,可以广泛应用于航空航天、飞机、汽车、微电子等领域。     

双烯丙基双酚A改性内扩链双马来酰亚胺研究

采用自制的叔丁基二胺单体1,4-双(4-氨基苯氧基)-2-叔丁基苯(BATB)与双酚A二酐(BPADA)反应,并以马来酸酐作为封端剂得到了一系列链中含酰亚胺环的内扩链双马来酰亚胺,将所得双马来酰亚胺混合双烯丙基双酚A(BBA)制得无胶型挠性覆铜板。采用傅里叶变换红外光谱(FTIR)、核磁共振氢谱(1H-NMR)、凝胶渗透色谱(GPC)、示差扫描量热法(DSC)和热重分析(TGA)对合成的封端聚酰亚胺树脂的结构进行了表征并测试了其性能,研究了BBA用量及加入前后对封端聚酰亚胺基膜力学性能、热性能、聚酰亚胺树脂固化性能的影响。结果表明,BBA与封端聚酰亚胺物质的量比为1∶1时,其增韧改性效果最佳。加入BBA后的薄膜在不降低热性能的情况下,力学性能提高(拉伸强度可达到67.14 MPa,弹性模量达到1 449.73 MPa,断裂伸长率最大达到6.17%)。所得两层型挠性覆铜板具有优异的耐热性、尺寸稳定性、低吸水率。     

均苯型共聚聚酰亚胺薄膜的制备及其性能

以2,2′-双[3-苯基-4(4-氨基苯氧基)苯基]丙烷(BPAPOPP)、4,4′-二胺基二苯醚和均苯四甲酸酐为原料,采用两步法共缩聚制备了一系列共聚聚酰亚胺薄膜.采用红外光谱仪、差示扫描量热仪等分析了薄膜的结构,利用静态热机械分析仪分析了薄膜的性能.结果表明:制备的聚酰亚胺薄膜具有较低的玻璃化转变温度;随着BPAP...     

Modification of negative auto‐photosensitive polyimide

This article describes the preparation of a kind of auto‐photosensitive polyimide (PSPI) that contains organo‐silicone moiety in its main chain. A group of novel auto‐photosensitive polyimides were prepared based on the aromatic diamine monomers and 3,3′,5,5′‐benzophenontetracarboxylic dianhydride (BTDA) by the method of solution polycondensation at room temperature and imidized at a high temperature. The properties of PSPIs, such as ultraviolet (UV) absorption, electric and adhesion properties, and moisture absorption, were characterized by UV analysis, a dielectric constant detector, and so on. The relationship between the structure and properties of PSPIs is discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 943–947, 2000     

Main-chain photosensitive polyamic acids using alkaline aqueous solution as developer

In order to develop photosensitive polyimides (PSPIs) imaged in alkaline aqueous solution, a photosensitive diamine and relevant polymer containing conjugated double bonds in the main chain have been synthesized. The photosensitive characteristics and thermal stability of the polymers were investigated. These polymers possess good thermal stability and sensitivity to UV irradiation, and could be used to form a PSPI resist using alkaline aqueous solution as developer. © 1999 Society of Chemical Industry     

Synthesis and characterization of novel negative-working aqueous base developable photosensitive polyimide precursors

Through molecular designing, three poly(amic esters) (PAEs) have been synthesized from pyromellitic dianhydride (PMDA), 2,2′-bis-(3-amino-4-hydroxyphenyl) hexafluoropropane (BisAPAF), 4,4′-diaminodiphenyl ether (4,4′-ODA) and 2-hydroxyethyl methacrylate (HEMA). Due to the introduction of photosensitive acrylate groups and aqueous base soluble phenolic hydroxyl groups in the backbone, these poly(amic esters) can be used as the precursors of negative-working, aqueous base developable photosensitive polyimides (PSPIs). These poly(amic esters) were prepared by direct polymerization by using phenyl phosphonic dichloride (PPD) as an activator. The inherent viscosities of these polymers were 0.20 (dL/g). Their structures were characterized by Fourier transform infrared spectroscopy (FTIR) and ¹H NMR. In order to improve the photolithographic performance of these PSPIs, different photosensitizers, photoinitiators and a crosslinker have been added in the PSPI formulations. Among them, the Michler's ketone (MK)/tribromomethyl phenyl sulfone (TBPS) system gave the best results. Using a 2.38 wt% aqueous TMAH solution as a developer, patterns with a resolution of 10 μm were obtained from these PSPI formulations. In addition, the effects of the molecular structure of the precursors and the concentration of developer on the photosensitivity of the PSPI formulations were also discussed.     

Novel auto-photosensitive polyimides with tailored properties

An overview is given on auto-photosensitive polyimides as introduced for the first time in 1985. It is shown how development proceeded and how the chemical basis of auto-photosensitive polyimides was extended beyond BTDA. Novel “photosensitizer tetracarboxylic dianhydrides” like 2,3,6,7-thioxanthonetetracarboxylic dianhydride (TXDA) were synthesized and copolymerized into preimidized nonphotoactive polyimides containing tetracarboxylic acids like 6FDA or ODPA. Novel photosensitive polyimides were obtained that carry all essential features of BTDA based systems plus higher photospeed. They provide the ability to better tailor material properties to specific applications.     

Photosensitive polyimide/silica hybrid optical materials: Synthesis, properties, and patterning

In conventional ionic salt photosensitive polyimides, large volume shrinkage during imidization would be occurred due to eliminating pendant photosensitive moieties, such as 2-methyl acrylic acid 2-dimethylamino-ethyl ester (MDAE). In this study, the volume shrinkage of photosensitive poly(4,4′-(hexafluoroisopropylidenediphthalic anhydride)-co-oxydianiline) (6FDA-ODA)/MDAE was largely reduced by photocrosslinking MDAE with a coupling agent and the silica domain in the hybrid materials. The used coupling agents were 3-methacryloxypropyl trimethoxysilane (MPTMS) or (4-vinylphenethyl)trimethoxysilane (VPTMS). The coupling agent and the silica domain are designed primarily for reducing the volume shrinkage and enhancing the thermal properties, respectively. The retention of MDAE in the prepared hybrid films is supported by X-ray photoelectron spectroscopy (XPS) and thickness variation during curing process. The silica domain in the hybrid materials from TEM analysis was in the range of 10-50 nm, which was formed by the coupling agent and tetramethoxysilane. The silica domain significantly enhanced the thermal properties of the prepared hybrid films in comparison with parent fluorinated polyimide, including the glass transition temperature and coefficient of thermal expansion. The prepared hybrid materials also exhibited reduced refractive index and optical loss by increasing the silica. The SEM diagram suggested the prepared photosensitive hybrid materials could obtain lithographical patterns with a good resolution. These results indicate that the newly prepared photosensitive polyimide/silica hybrid materials may have potential applications for optical devices.     

Synthesis and characterization of a low stress photosensitive polyimide

Use of polyimides with thermal coefficients of expansion comparable to that of the underlying substrate is critical to achieving low stress in microelectronic packaging applications. Photosensitive polyimides are finding increased use because of their significant reduction in device processing steps. A negative working photosensitive polyimide, based on the BPDA/PPD backbone, has been synthesized that incorporates these key features. The polyimide exhibits excellent photosensitivity and lithographic behavior, while retaining many thermal and physical properties of the polymer framework.     

Intrinsically photosensitive polyimides: Approaches to fluorinated homologs

Cyclobutane tetracarboxylic acid dianhydrides, which were prepared via photodimerization of maleic anhydride or methylmaleic anhydride, gave high molecular weight film-forming polyimides with oxydianiline. The resulting polyimides were found to be photosensitive, presumably because of retrocyclization of the cyclobutane ring. Despite the presence of the cyclobutane ring, the polyimides show good thermal stability. In an effort to enhance the thermal stability and lower the dielectric constant of these polyimides, an approach was made to prepare the fluorinated analogs of the cyclobutane dianhydride monomers via the preparation and photodimerization of fluorinated maleic anhydride derivatives. Thus, both fluoromaleic and difluoromaleic anhydrides were photolyzed to give the target monomers. The proposed application of these monomers, however, has yielded disappointing results due to complications in their synthesis and attempted polymerization.     

Photosensitive polyimides developable with basic aqueous solutions (II)

Positive and negative photosensitive polyimides developable with basic aqueous solutions are reported. The results consist of poly amic acids and naphthoquinone diazides in which sulfonate groups have to be substituted at 4-position. It depends on the naphthoquinone structures whether positive or negative patterns are obtained. In order to fabricate resist patterns, High-Temperature-Post-Exposure-Process (HIT-PEB) must be utilized. The reaction mechanisms are also discussed. © 1992 John Wiley & Sons, Inc.     

A novel positive‐type photosensitive polyimide having excellent transparency based on soluble block copolyimide with hydroxyl group and diazonaphthoquintone

A novel positive‐type photosensitive polyimide having excellent transparency based on soluble block copolyimide (Bco‐PI) with hydroxyl group and diazonaphthoquinone (DNQ) as a photoreactive compound was developed. The base Bco‐PI A was prepared by a direct one‐pot polycondensation of cyclohexanetetracarboxylic dianhydride (H‐PMDA), 2,2‐bis(3‐amino‐4‐hydroxyphenylhexafluoropropane) (Bis‐AP‐AF), and bis(4‐(3‐aminophenoxy)phenyl)sulfone (m‐BAPS) in the presence of a γ‐valerolactone and pyridine catalyst system by using dipolar aprotic solvent such as N‐methyl‐2‐pyrrolidone (NMP).The wholly aromatic polyimides have strong absorptions in the visible regions, because of their change–transfer complex formation. On the other hand, alicyclic dianhydride, H‐PMDA, contributed to the resulting Bco‐PI film with colorlessness and transparency, which are the important factors for a photosensitive polyimide. Photosensitive Bco‐PI, containing 20 wt % 1,2‐naphthoqiunonediazide‐5‐sulfonic acid p‐cresol ester (PC5), showed a sensitivity of 250 mJ/cm² and a contrast of 2.56 when it was exposed to UV light, followed by development with 5% tetramethylammonium hydroxide (TMAH) aqueous solution at room temperature. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1619–1624, 2005     

Synthesis and properties of new photosensitive and chiral poly(amide‐imide)s based on bicyclo[2,2,2]oct‐7‐ene‐2,3,5,6‐tetracarboxylic diimide and dibenzalacetone moieties in the main chain

Aromatic poly(amide‐imide)s (PAIs) are high‐performance materials with a good compromise between thermal stability and processability when compared with polyamides or polyimides of analogous structures. In addition, the incorporation of photosensitive functional groups and chiral segments into the polymer backbone can lead to interesting polymers for various applications. In this work, six new photosensitive and chiral PAIs were synthesized from the direct polycondensation reaction of novel N,N′‐(bicyclo[2,2,2]oct‐7‐ene‐tetracarboxylic)‐bis‐L ‐amino acids with 2,5‐bis(4‐aminobenzylidene)cyclopentanone as dibenzalacetone moiety using two different methods. The polymerization reactions produced a series of photosensitive and optically active PAIs in high yields and with good inherent viscosities. The resulting polymers were characterized using Fourier transform infrared and ¹H NMR spectroscopy, elemental analysis, inherent viscosity, specific rotation, solubility tests and UV‐visible spectroscopy. The thermal properties of the PAIs were investigated using thermogravimetric analysis. Due to the presence of the dibenzalacetone moiety in the polymer chain, the PAIs have photosensitive properties. Also, these PAIs are optically active and soluble in various organic solvents. These resulting new polymers have the potential to be used in column chromatography for the separation of enantiomeric mixtures. Copyright © 2009 Society of Chemical Industry