TW200906910A - Precursor for polyimide and use thereof - Google Patents

Precursor for polyimide and use thereof Download PDF

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TW200906910A
TW200906910A TW096128743A TW96128743A TW200906910A TW 200906910 A TW200906910 A TW 200906910A TW 096128743 A TW096128743 A TW 096128743A TW 96128743 A TW96128743 A TW 96128743A TW 200906910 A TW200906910 A TW 200906910A
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TWI435893B (en
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Chung-Jen Wu
Shun-Jen Chiang
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Eternal Chemical Co Ltd
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Priority to JP2008200120A priority patent/JP5437604B2/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/67—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
    • C07C233/75—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
    • 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
    • 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

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The present invention provides a precursor for polyimides. The precursor has the structure of formula (1) wherein R, Rx, G, P, and m are as defined in the specification. The present invention also provides a polyimide prepared from the precursor. The polyimide exhibits excellent operative characteristics and physiochemical properties.

Description

200906910 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種新穎聚醯亞胺之前驅物，本發明亦關 於該新穎聚醯亞胺之前驅物於製備聚醢亞胺（p〇lyimide， 簡稱pi)之應用。 【先前技術】 聚醯亞胺由於具有優異的熱安定性及良好的機械、電氣 及化學性質’一直是咼性能高分子材料的首選。此外，由 於半導體在特性上的要求越來越高，而傳統無機材料有其 應用上的極限及缺點，聚醯亞胺的特性，在某些方面正可 以彌補傳統材料的不足之處。因此，當杜邦公司之芳香族 聚醯亞胺技術開發之後，即受到廣泛的注意，且發展出許 多具多用途的聚醯亞胺。 在半V體工業上，聚醯亞胺被廣泛應用於純化膜、應力 緩衝膜、OC粒子遮蔽膜、乾式蝕刻防護罩、微機電和層間 絕緣膜等方面，且正陸續開發出其他新用途。其中，以作 為保積體電路元件之塗膜的應用為大宗，因聚醯亞胺材 料可通過積體電路元件可靠性之測試。惟，聚醯亞胺之應 用不僅只於積體電路工業，其於電子構裝、漆包線、印刷 電路板、感測元件、分離膜及結構材料上都相當重要，扮 演著關鍵性材料的角色。 般係以—1¾奴之聚合縮合反應方式以合成聚醯亞胺。 其中’通常於第-階段將二胺單體溶於如N_甲基D比略闕 (NMP)、—曱基乙酿胺（DMAC)、二曱基曱醯胺（dmf)或二 122330.doc 200906910 甲基亞砜（DMSO)之極性、非質子性溶劑中，再加入等莫 耳二酸酐單體。其後，於低溫或常溫下進行縮合反應’形 成聚醯亞胺前驅物（precursor)，即，聚醯胺酸（P〇ly(amic acid);簡稱為 PAA)。 接著，進行第二階段，藉由加熱方式的醯亞胺化 (thermal imidization)或化學方式的醯亞胺化（chemical imidization)，進行縮合脫水環化反應，將聚醯胺酸轉變為 聚醯亞胺。 目前製備聚醯亞胺之反應流程可簡述如下：200906910 IX. INSTRUCTIONS: [Technical Field] The present invention relates to a novel polyimine precursor, and the invention also relates to the novel polyimine precursor to prepare polyimine (p〇lyimide) , referred to as pi) application. [Prior Art] Polyimine has always been the first choice for high performance polymer materials due to its excellent thermal stability and good mechanical, electrical and chemical properties. In addition, due to the increasing requirements of semiconductors in terms of characteristics, and traditional inorganic materials have their application limits and shortcomings, the properties of polyimine can compensate for the shortcomings of traditional materials in some aspects. Therefore, when DuPont's aromatic polyimine technology was developed, it received extensive attention and developed many versatile polyimine. In the semi-V body industry, polyimine is widely used in purification membranes, stress buffer membranes, OC particle shielding membranes, dry etching shields, microelectromechanical and interlayer insulating films, and other new applications are being developed. Among them, the application as a coating film for the circuit element of the bulking body is bulky, and the polyimide material can be tested for the reliability of the integrated circuit component. However, the application of polyimine is not only in the integrated circuit industry, but also plays an important role in electronic construction, enameled wire, printed circuit boards, sensing components, separation membranes and structural materials. In general, a polycondensation is carried out by a polymerization condensation reaction method of -13⁄4 slave. Wherein 'usually in the first stage, the diamine monomer is dissolved in, for example, N_methyl D than sputum (NMP), fluorenyl ethanoamine (DMAC), decyl decylamine (dmf) or two 122,330. Doc 200906910 In a polar, aprotic solvent of methyl sulfoxide (DMSO), an additional molar anhydride monomer is added. Thereafter, the condensation reaction is carried out at a low temperature or a normal temperature to form a polyimide precursor, i.e., P〇ly (amic acid; abbreviated as PAA). Then, in the second stage, the condensed dehydration cyclization reaction is carried out by a thermal imidization or a chemical imidization method to convert the polylysine into a poly amine. The current reaction scheme for preparing polyimine can be briefly described as follows:

H2N—Αγ'*ΝΗ2H2N—Αγ'*ΝΗ2

如第一階段所得之聚醯胺酸分子量 於上述製備方法中 未達"'定標準（即’分子量過小），於醯亞胺化（imidization) 後二無法得到具良好物性之聚醯亞胺膜。$，若第一階段 所得聚醯胺酸之分子量過高，則其黏度便會太大，以致於 操作性變差’易於塗佈時有流平性不良等缺點。舉例言 之，於進行旋轉塗佈時，容易產生中凸與厚邊等不易流平 見象此外’過高之聚_胺酸分子量，將於進行第二階段 122330.doc 200906910 之醯亞胺化時，因分子間之交互作用以及分子鍵鍵長的縮 短，產生極大内應力，致使所塗佈之基材彎曲變形。因 此，為免除前述問題’文獻上業已廣泛探討第二階段醯亞 胺化之升溫梯度曲線與内應力關係，並研究出各式降低内 應力之方式。然而，前述流平性與内應力問胃，究其原 因，均來自第一階段所得聚醯胺酸分子量過高所致。換言 Ο Ο 之’若能妥善控制聚醯胺酸分子量，便可提供具優良物性 之聚醯亞胺膜。 此外，聚醯胺酸相當容易吸濕，進而使聚醯胺酸與水分 子反應而降解，故不易保存。 上述問題’多年來持續困擾著從事聚醯亞胺研究之人 士 ’蓋材料特性與操作性之間往往存在衝突，無法兼得。 本發明即針對前述問題所為之研發成果，藉由特殊之合成 方式’可於兼顧操作性之情形下，提供具所欲物性之聚醯 亞胺膜，符合業界之需求。 【發明内容】 的聚醯亞胺之前驅 物 本發明之一目的在於提供一種新穎 本發明之另一目的在协担 *於鈇供一#包含上述前驅物之組合 物。 聚醯亞胺之方法。 =式又】一目的在於提供—種製備 本發明聚醯亞胺 酯寡聚物： 之前驅物係具下式⑴之結構之醯胺酸 122330.doc 200906910If the molecular weight of the poly-proline obtained in the first stage does not reach the standard in the above preparation method (ie, the molecular weight is too small), the polyimine with good physical properties cannot be obtained after the imidization. membrane. If the molecular weight of the polyamic acid obtained in the first stage is too high, the viscosity thereof will be too large, so that the workability is deteriorated, and it is easy to apply a defect such as poor leveling. For example, when spin coating is applied, it is easy to produce a convex and thick edge, etc., which is difficult to level up. In addition, the molecular weight of the poly-amino acid which is too high will be subjected to the second stage 122330.doc 200906910. At the time, due to the interaction between molecules and the shortening of the molecular bond length, a great internal stress is generated, causing the coated substrate to be bent and deformed. Therefore, in order to avoid the aforementioned problems, the relationship between the temperature gradient curve and the internal stress of the second-stage ruthenium has been extensively studied in the literature, and various ways of reducing the internal stress have been studied. However, the above-mentioned leveling and internal stress are all related to the stomach, and the reason is derived from the excessive molecular weight of the polylysine obtained in the first stage. In other words, if the molecular weight of poly-proline is properly controlled, a polyimide film with excellent physical properties can be provided. In addition, polylysine is relatively easy to absorb moisture, which in turn causes the polyamine to react with water to degrade and is therefore difficult to store. The above-mentioned problems have been plagued by people who have been engaged in polyimine research for many years. There is often a conflict between the characteristics of materials and the operability of the cover materials. The present invention is directed to the research and development of the above problems, and the special synthetic method can provide a desired polyimide film with the desired properties, which meets the needs of the industry. SUMMARY OF THE INVENTION Polyimine precursors of the present invention It is an object of the present invention to provide a novel composition of the present invention in which a further object of the present invention is to coexist. The method of polyimine. The purpose of the present invention is to provide a preparation of the polyimine ester oligomer of the present invention: a precursor of a proline having the structure of the following formula (1) 122330.doc 200906910

其中 R為具1至14個碳原子之直鏈或支鏈烷基、具6至14個 碳原子之芳基或芳烷基或乙烯系不飽和基；Wherein R is a linear or branched alkyl group having 1 to 14 carbon atoms, an aryl or aralkyl group having 6 to 14 carbon atoms or an ethylenically unsaturated group;

Rx各自獨立為Η或可感光聚合之基團； G各自獨立為4價之有機基團； P各自獨立為2價之有機基團；以及 m係0至1〇〇之整數。 根據本發明之一具體實施態樣，上述式（1)中之尺係具丄 〇 至14個碳原子之直鏈或支鏈烷基，其例如為具以下結構之 直鏈或支鏈烷基：Each of Rx is independently a photopolymerizable group; G is each independently a tetravalent organic group; P is each independently a divalent organic group; and m is an integer of 0 to 1 Å. According to an embodiment of the present invention, the ruler of the above formula (1) has a linear or branched alkyl group of up to 14 carbon atoms, which is, for example, a linear or branched alkyl group having the following structure :

其中η係0至10之整數。該具1至14個碳原子之直鏈或支鍵 烷基之具體實例包含（但不限於）曱基、乙其 田 U丞、正丙基、異 丙基、1-甲基丙基、2-曱基丙基、正丁基、異丁美 122330.doc 200906910 (isobutyl )、新丁基（tert_butyl) ' κ 甲基丁基、2-甲基丁 基、戊基、己基、庚基及辛基等。 前述具6至14個碳原子之芳基或芳烧基，較佳為選自由 下列基團所構成群組： 、~~<〇v~cH3 及Wherein η is an integer from 0 to 10. Specific examples of the linear or branched alkyl group having 1 to 14 carbon atoms include, but are not limited to, anthracenyl, ethylidene, n-propyl, isopropyl, 1-methylpropyl, 2- Mercaptopropyl, n-butyl, isobutylene 122330.doc 200906910 (isobutyl), neobutyl (tert_butyl) ' κ methyl butyl, 2-methyl butyl, pentyl, hexyl, heptyl and octyl Wait. The above aryl or aryl group having 6 to 14 carbon atoms is preferably selected from the group consisting of: ~~<〇v~cH3 and

CHa Γ ϋ 上述乙稀系不飽和基，並無特殊限制，其實例包括（但 不限於）乙稀基、丙烯基、甲基丙烤基、正丁稀基、異丁 稀基、乙縣苯基、丙縣苯基、丙烯氧基甲基、丙婦氧 基乙基、丙烯氧基丙基、丙稀氧基丁基、丙稀氧基戍基、 丙烯氧基己基、甲基丙稀氧基甲I、甲基丙烯氧基乙基、 甲基丙婦氧基丙基、f基丙職基丁基、甲基丙烯氧基戍 基、及甲基丙烯氧基己基、以及如式⑺所示之基團 f?2 〇 h2c=4」丨—。一Ri___ (2) 其中，R,為伸苯基、（：3-〇：8伸環烧基、直鏈或支鏈2CiC8 伸炫基、ca伸稀基、或Ci_C8m基伸燒基，且&為氣或 Cj-C4烷基。其中，較佳之式（2)基團可為： ch3o h2c=c—c—ο— c2h4- Η2α ίί -ο—C2H4—、CHa Γ ϋ The above ethylenically unsaturated group is not particularly limited, and examples thereof include, but are not limited to, ethylene, propylene, methyl propyl, n-butyl, isobutyl, and benzene. Base, phenyl phenyl, propyleneoxymethyl, propyl ethoxyethyl, propyleneoxypropyl, propyloxy butyl, propyloxy fluorenyl, propyleneoxyhexyl, methyl propyloxy a group I, a methacryloxyethyl group, a methyl propyl ethoxypropyl group, a f-propyl propyl butyl group, a methacryloxy fluorenyl group, and a methacryloxyhexyl group, and a formula (7) The group shown is f?2 〇h2c=4"丨-. A Ri___ (2) wherein R is a phenylene group, (: 3-〇:8 stretching ring group, a linear or branched 2CiC8 stretching group, a ca stretching group, or a Ci_C8m group stretching group, and & Is a gas or Cj-C4 alkyl group. Among them, the preferred group of formula (2) can be: ch3o h2c=c-c-ο- c2h4- Η2α ίί -ο-C2H4-,

QfV HI CIC II c 2 HQfV HI CIC II c 2 H

2 H2 H

CHlOHCHlOH

2 H C—H li c H2 或 Η22 H C—H li c H2 or Η2

CH—OH Η2 122330.doc 200906910 上述式（υ中之基團1可各自獨立為H或任何具有可感光 聚合之基團，該可感光聚合之基團較佳為含有如上文所定 義之乙烯系不飽和基之基團。根據本發明，基團Rx較佳各 自獨立為Η、甲基丙烯酸_2·羥基丙酯基、甲基丙烯酸乙酯 基、丙烯酸乙酯基、丙烯基、甲基丙烯基、正丁烯基或異 丁烯基，更佳各自獨立為Η或甲基丙烯酸_2_羥基丙醋基： CH30 H2C= c— c— 0— CH2- ch— ch2—CH—OH Η2 122330.doc 200906910 The above formula (the group 1 in the oxime may each independently be H or any group having a photopolymerizable group, and the photosensitive polymerizable group preferably contains a vinyl group as defined above. The group of the unsaturated group. According to the invention, the groups Rx are preferably each independently hydrazine, hydroxypropyl methacrylate, ethyl methacrylate, ethyl acrylate, propylene, methacryl Base, n-butenyl or isobutenyl, more preferably each independently hydrazine or methacrylic acid 2_hydroxypropyl acrylate: CH30 H2C= c- c- 0-CH2-ch-ch2-

I 0I 0

OH 本發明式⑴醯胺酸醋募聚物所含之4價有機基團G，並 …特殊限制’其例如為4價之芳香族基團或4價之脂肪族基 團。前述芳香族基團可為單環或多環，較佳為選自由下列 基團所構成群組：OH The tetravalent organic group G contained in the glycine vinegar condensate of the formula (1) of the present invention is specifically limited to, for example, a tetravalent aromatic group or a tetravalent aliphatic group. The aforementioned aromatic group may be monocyclic or polycyclic, and is preferably selected from the group consisting of the following groups:

田斤、Li-C4全氟烷基或C丨_C4烷Tian Jin, Li-C4 perfluoroalkyl or C丨_C4

其中γ各自獨立為氫、鹵素、 基，及 B 為·CH2-、-〇-、^ _C(CV . 、-S02-、-C(CH3)2-或 ’更佳為選自由下列基團所構成群組：Wherein γ is independently hydrogen, halogen, or the group, and B is ·CH2-, -〇-, ^_C(CV., -S02-, -C(CH3)2- or 'more preferably selected from the group consisting of Form a group:

122330.doc 10- 200906910 根據本發明，上述4價 成群組 脂肪族基可選自由下列基團所構122330.doc 10-200906910 According to the present invention, the above tetravalent group of aliphatic groups may be selected from the following groups.

本發明式⑴醯胺酸酯寡聚物所含之2價有機基團P，並 無特殊限制’其通常為芳香族基團，較佳各自獨立為 〇The divalent organic group P contained in the phthalate oligomer of the formula (1) of the present invention is not particularly limited. It is usually an aromatic group, and preferably each independently is 〇

佳地，該2價有機基團P係各自獨立為 OC(O)·或-CONH-。更Preferably, the divalent organic group P is independently OC(O)· or -CONH-. more

或or

ch2Ch2

於較佳具體實施態樣中，該2價有機基團p係In a preferred embodiment, the divalent organic group p is

XT 上述2價有機基團P，亦可為非芳香族基團，例如 -CH：XT The above divalent organic group P may also be a non-aromatic group, such as -CH:

X ch2- 122330.doc -11· 200906910 其中，χ係如前文所定義；以及w&z各自為丨至3之整數 較佳地’該2價有機基團p為 H3CpH： ch2- -CH2 -Si—〇—-Si- h3 本案發明人發現，不同於先前技藝用以製備聚醯亞胺之 聚醢胺酸前驅物，上述式⑴醯胺酸酯募聚物由於酸基減 少，故較不會吸濕，即使吸溼，亦較穩定，故可於室溫下 保存備用，無需儲存於低溫（如：零下20。〇。 發月之酿版酸醋券聚物可藉本發明所屬技術領域中具 有通常知識者所習知的聚合方法獲得，例如可藉由包含下 列步驟之方法製得： U)使一具下式（3)之二酸酐與具羥基之化合物反 應’形成具下式（4)之化合物；以及X ch2- 122330.doc -11· 200906910 wherein, the lanthanide is as defined above; and w&z is each an integer from 丨 to 3, preferably 'the divalent organic group p is H3CpH: ch2- -CH2 -Si —〇—Si— h3 The inventors of the present invention have found that, unlike the poly-proline precursors previously prepared for the preparation of polyimine, the above-mentioned formula (1) phthalate condensate is less likely to be due to a decrease in acid groups. Moisture absorption, even if it is hygroscopic, it is stable, so it can be stored at room temperature for use without storage at low temperature (eg: minus 20. 〇. The vinegar vinegar granules can be used in the technical field of the invention) It is obtained by a polymerization method known to those skilled in the art, for example, by a method comprising the following steps: U) reacting a dianhydride of the following formula (3) with a compound having a hydroxyl group to form a formula (4) a compound; and

(b)於步驟⑷產物中添加具式H2N-P-NH2之二胺化合 物’形成式（5)醯胺酸酯寡聚物。(b) adding a diamine compound of the formula H2N-P-NH2 to the product of the step (4) to form a guanamine oligomer of the formula (5).

HzN—P—NH2HzN—P—NH2

OH OH 人G人 0R 122330.doc •12- (5)。 200906910 圏（R*)之單體，例如環 進行反應，形成式（6)醯 (C)視情況添加帶有可感光聚合基 乳丙婦酸酯（epoxy acrylate)， 胺酸酯寡聚物，OH OH person G person 0R 122330.doc •12- (5). 200906910 A monomer of ruthenium (R*), such as a ring, is reacted to form a formula (6) 醯 (C) optionally with an operably polymerizable epoxy acrylate, an amine acrylate oligomer,

其中R、G及P係如前文所定義，a、b、及f各為〇至1〇〇之整 數，且 a+bS100。 於上述製備式（1)醯胺酸酯寡聚物之方法中，步驟（a)所 使用之一酸酐’ 一般可為脂肪族或芳香族者，較佳為芳香 族一酸針’其實例包括（但不限於）均笨四酸二酐（PMda)、 4,4，-二酞酸二酐（BPDA)、4,4，-六氟亞異丙基二酞酸二酐 (6FDA)、1-(三氟甲基）-2,3,5,6-苯四級酸二酐（P3FDA)、二Wherein R, G and P are as defined above, and a, b, and f are each an integer from 〇 to 1〇〇, and a+bS100. In the above process for preparing the phthalate oligomer of the formula (1), the anhydride used in the step (a) is generally an aliphatic or aromatic, preferably an aromatic acid needle. Examples thereof include (but not limited to) Ductotetracarboxylic dianhydride (PMda), 4,4,-diphthalic acid dianhydride (BPDA), 4,4,-hexafluoroisopropylidene diacetate dianhydride (6FDA), 1 -(trifluoromethyl)-2,3,5,6-benzene tetracarboxylic acid dianhydride (P3FDA), two

苯甲酮-四羧酸二酐（BTDA)、3,3，，4,4，-二苯醚四羧酸二針 (ODPA)、M-雙（三氟甲基）-2,3,5,6-苯四羧酸二肝 (P6FDA)、1-(3，，4，-二羧基苯基）-1,3,3-三甲基節滿 _5,6_二 羧酸二酐、卜（3\4’-二羧基苯基）-1,3,3-三甲基茚滿_6,7_二 幾·酸二針、1_(3'，4^ -二叛基苯基）-3-甲基節滿-5,6 -二缓酸二 酐、1-(3'，4·-二羧基苯基）-3-甲基茚滿-6,7-二羧酸二酐、 2,3,9,10-二萘嵌苯四羧酸二酐、1，4,5,8-萘四羧酸二酐、 2,6-二氯萘-1,4,5,8-四羧酸二酐、2,7-二氯萘-1，4,5,8-四缓 酸二酐、2,3,6,7-四氯萘-2,4,5,8-四羧酸二酐、菲·mjo-四叛酸二酐、3，3'，4,4’-二苯甲酮四叛酸二酐、1,2，,3，3，-二 122330.doc .13- 200906910Benzene-tetracarboxylic dianhydride (BTDA), 3,3,,4,4,-diphenyl ether tetracarboxylic acid two-needle (ODPA), M-bis(trifluoromethyl)-2,3,5 , 6-benzenetetracarboxylic acid di-hepatic (P6FDA), 1-(3,4,-dicarboxyphenyl)-1,3,3-trimethyl-consumer-5,6-dicarboxylic dianhydride, Bu(3\4'-dicarboxyphenyl)-1,3,3-trimethylindan _6,7_di-acidic acid two-needle, 1_(3',4^-di-repentylphenyl) -3-methyl-negative-5,6-di-hypo-dianhydride, 1-(3',4-dicarboxyphenyl)-3-methylindan-6,7-dicarboxylic dianhydride, 2,3,9,10-perylene tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetra Carboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetrazoic acid dianhydride, 2,3,6,7-tetrachloronaphthalene-2,4,5,8-tetracarboxylic acid Dianhydride, phenanthrene mjo-tetra-rebel dianhydride, 3,3',4,4'-benzophenone tetrahydro acid dianhydride, 1,2,3,3,-two 122330.doc .13- 200906910

苯甲酮四羧酸二酐、3,3’,4,4’-聯苯四叛酸二酐、3,3'，4,4'-二苯甲酮四叛酸二酐、2,2’，3,3'-聯苯四叛酸二酐、4,4'-亞 異丙基二酞酸二酐、3，3’-亞異丙基二酞酸二酐、4,4'-氧基 二酞酸二針、4,4'-續醯基二酜酸二酐、3,3，_氧基二献酸二 酐、4,4'-亞甲基二欧酸二酐、4,4，-硫基二欧酸二酐、4,4'-亞乙基二酜酸二酐、2,3,6,7-萘四叛酸二酐、1，2,4,5-萘四 羧酸二酐、1，2,5,6-萘四羧酸二酐、苯4,2,3,4-四羧酸二 酐、吡啶-2,3,5,6-四羧酸二酐或其組合。 較佳地，係於步驟（a)採用選自以下群組之芳香族二酸 酐：均苯四酸二酐（PMDA)、4,4，-二欧酸二酐（BPDA)、 4,4'-六氟亞異丙基二酞酸二酐（6Fda)、1-(三氟甲基）-2,3,5,6-苯四羧酸二酐（P3FDA)、Μ·雙（三氟曱基）-2,3,5,6_ 苯四羧酸二酐（P6FDA)、二苯甲酮-四羧酸二酐（BTDA)、 3,3’，4,4'-二苯醚四羧酸二酐（〇dpa)及其混合物。於一具體 實施態樣中’係採用均苯四酸二酐（PMDA)。 可用於本發明方法以製備式（1)醯胺酸酯寡聚物之具羥 基之化合物，可為醇類，例如一元醇、二元醇或多元醇， 較佳為一元酵。可用於本發明之一元醇並無特殊的限制， 其可為烷基酵、芳烷基醇或芳基醇。舉例言之（但不以此 為限）’該一元醇可為具1至14個碳原子之直鏈或支鏈院基 醇’例如具以下結構之直鏈或支鏈烷基醇：Benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetrahydro acid dianhydride, 3,3',4,4'-benzophenone tetrahydro acid dianhydride, 2,2 ',3,3'-biphenyltetrahydro acid dianhydride, 4,4'-isopropylidenedicarboxylic acid dianhydride, 3,3'-isopropylidene dicarboxylic acid dianhydride, 4,4'- Two needles of oxydiconate, 4,4'-continuous decyl diphthalic acid dianhydride, 3,3,-oxydiacid dianhydride, 4,4'-methylene dioic acid dianhydride, 4 , 4,-thiodicarboxylic acid dianhydride, 4,4'-ethylene dicarboxylic acid dianhydride, 2,3,6,7-naphthalene tetra-retensive dianhydride, 1,2,4,5-naphthalene Tetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, benzene 4,2,3,4-tetracarboxylic dianhydride, pyridine-2,3,5,6-tetracarboxylic acid Anhydride or a combination thereof. Preferably, in step (a), an aromatic dianhydride selected from the group consisting of pyromellitic dianhydride (PMDA), 4,4,-dioxalic acid dianhydride (BPDA), 4, 4' is used. - hexafluoroisopropylidene dicarboxylic acid dianhydride (6Fda), 1-(trifluoromethyl)-2,3,5,6-benzenetetracarboxylic dianhydride (P3FDA), bismuth (trifluorofluorene) Base-2,3,5,6_ benzenetetracarboxylic dianhydride (P6FDA), benzophenone-tetracarboxylic dianhydride (BTDA), 3,3',4,4'-diphenyl ether tetracarboxylic acid Diacid anhydride (〇dpa) and mixtures thereof. In a specific embodiment, pyromellitic dianhydride (PMDA) is used. The compound of the present invention which can be used in the process of the present invention to prepare a hydroxyl group of the phthalate oligomer of the formula (1) may be an alcohol such as a monohydric alcohol, a dihydric alcohol or a polyhydric alcohol, preferably a monohydric yeast. The monool which can be used in the present invention is not particularly limited and may be an alkyl yeast, an aralkyl alcohol or an aryl alcohol. By way of example (but not by way of limitation), the monohydric alcohol may be a linear or branched anhydride alcohol having from 1 to 14 carbon atoms, such as a linear or branched alkyl alcohol having the following structure:

122330.doc 14· 200906910 其中，η為〇至10之整數.於此，該具丨至14個碳原子之直 鏈或支鏈烷基醇包括（但不限於）甲醇、乙醇、正丙醇、異 丙醇、1·甲基丙_、正丁醇、異丁醇、新丁醇、r甲基丁 西子、2-甲基丁醇、戊醇、己醇、庚醇及辛醇。該一元醇亦 可為具6至14個碳原子之芳烷基醇或芳基醇，例如具以下 結構之芳烧基醇或芳基醇：122330.doc 14· 200906910 wherein η is an integer from 〇 to 10. Here, the linear or branched alkyl alcohol having from 丨 to 14 carbon atoms includes, but is not limited to, methanol, ethanol, n-propanol, Isopropanol, 1-methylpropanol, n-butanol, isobutanol, neobutanol, r-methylbutyro, 2-methylbutanol, pentanol, hexanol, heptanol, and octanol. The monohydric alcohol may also be an aralkyl alcohol or an aryl alcohol having 6 to 14 carbon atoms, such as an aryl alcohol or an aryl alcohol having the following structure:

h〇-<^-ch3 及H〇-<^-ch3 and

ch3 可用於本發明方法中之具羥基之化合物亦可帶有可感光 之基團，例如乙烯系不飽和基，較佳為具下式（7)者： R2 〇 —| || ⑺，Ch3 The compound having a hydroxyl group which can be used in the method of the present invention may also have a photosensitive group such as an ethylenically unsaturated group, preferably those having the following formula (7): R2 〇 —| || (7),

H2C=c C——0 -OH 其中，I係伸苯基、CyC8伸環烷基或直鏈或支鏈之 伸烷基、c^-c：8伸烯基或Cl_C8羥基伸烷基，且R2係氫或Ci_ C4烷基。較佳地，式（7)化合物係選自以下群組：丙烯酸 2-經基乙 g旨（2-hydroxyethyl acrylate，HEA)、甲基丙稀酸 2-故基乙西旨（2-hydroxyethyl methacrylate , HEMA)、甲基 丙烯酸細水甘油g旨（glycidyl methacrylate，GMA)、丙稀酸 縮水甘油酯（glycidyl acrylate)、及其組合。 上述製備式（1)聚醯胺酸前驅物之方法中，步驟（b)所使 用之二胺’並無特殊限制，通常使用芳香族二胺。可用於 本發明方法之芳香族二胺，係熟悉此技術領域者所熟知。 122330.doc 15 200906910 舉例a之（但不以此為限）可選自以下群組：4,4，·氧化二苯 胺（ODA)、對苯二胺（pPDA)、間二甲基對二胺基聯苯 (DMDB)、間二（三氟甲基）對二胺基聯苯、鄰二甲 基對一胺基聯苯（〇TLD)、4,4，-八氟聯苯胺（〇FB)、四氟_ 對-苯一胺（TFPD)、2,2·_5,5,_四氯聯苯胺（tcb)、3,3·_二氯 聯苯胺（DCB)、2,2，-雙（3-胺基苯基）六氟丙烷、2,2，-雙（4_ 胺基苯基）六氟丙烷、4,4，-氧基-雙[3·(三氟甲基）苯胺、 3’5 一 私基二敦甲本（3，5-diaminobenzotrifluoride)、四氟 _ 1’4-伸本一胺（tetrafluorophenylene diamine)、四氟-間-伸 笨二胺、1,4-雙（4-胺基苯氧基）_2_第三丁基苯（batb)、 2,2’-二甲基-4,4'-雙（4-胺基苯氧基）聯苯（DBAPB)、2,2-雙 [4-(4-胺基苯氧基）苯基]六氟丙烧（BAPPH)、2，2，-雙[4-(4-胺基苯氧基）苯基]原冰片烷（BAPN)、5-胺基-1-(4，-胺基苯 基）-1，3,3-三甲基茚滿、6-胺基-1-(4’-胺基苯基）-1，3,3-三甲 基茚滿、4,4'-亞曱基雙（鄰-氯苯胺）、3,3·-二氣二苯胺、 3，3'-磺醯基二苯胺、4,4'-二胺基二苯甲酮、1,5-二胺基 萘、雙（4-胺基苯基）二乙基矽烷、雙（4-胺基苯基）二苯基矽 烷、雙（4-胺基苯基）乙基膦氧化物、N-(雙（4-胺基苯基））-N-甲基胺、N-(雙（4-胺基苯基）)-N-苯基胺、4,4’-亞甲基雙 (2-甲基苯胺）、4,4’-亞甲基雙（2-甲氧基苯胺）、5,5'-亞曱基 雙（2-胺基苯酚）、4,4’·亞甲基雙（2·曱基苯胺）、4,4’-氧基雙 (2-甲氧基苯胺）、4,4’-氧基雙（2-氣苯胺）、2,2’-雙（4-胺基苯 酚）、5,5，-氧基雙（2_胺基苯酚）、4,4'-硫基雙（2-甲基苯 胺）、4,4，-硫基雙（2-曱氧基苯胺）、4,4'-硫基雙（2-氣苯 122330.doc -16· 200906910 胺）、4,4'-磺醯基雙（2-曱基苯胺）、4,4’-磺醯基雙（2-乙氧基 苯胺）、4,4'-磺醯基雙（2-氯苯胺）、5,5|-磺醯基雙（2-胺基苯 酚）、3,3f-二甲基-4,4'-二胺基二苯甲酮、3,3’·二甲氧基-4,4’-二胺基二苯甲酮、3,3f-二氯-4,4’-二胺基二苯曱酮、 4,4’-二胺基聯苯、間-苯二胺、4,4’-亞甲基二苯胺（MDA)、 4，4'-硫基二本胺、4，4^績酿基一本胺、4,4'-亞異丙基二苯 胺、3,3’-二甲氧基聯苯胺、3,3’-二羧基聯苯胺、2,4_曱苯 基二胺、2，5 -甲苯基二胺、2,6-曱苯基二胺、間-二甲苯基 二胺、2,4_二胺基_5_氣甲苯、2,4-二胺基氯甲苯、及其 組合。較佳地，係採用4,4，_氧化二苯胺（〇DA)、對苯二胺 (pPDA)、間二甲基對二胺基聯苯（Dmdb)、間二（三氟甲H2C=c C——0 -OH wherein, I is a phenyl group, a CyC8 cycloalkyl group or a linear or branched alkyl group, a c--c:8-alkylene group or a Cl_C8-hydroxyl-alkyl group, and R2 is hydrogen or Ci_C4 alkyl. Preferably, the compound of the formula (7) is selected from the group consisting of 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (2-hydroxyethyl methacrylate) , HEMA), glycidyl methacrylate (GMA), glycidyl acrylate, and combinations thereof. In the above process for producing the polyglycine precursor of the formula (1), the diamine used in the step (b) is not particularly limited, and an aromatic diamine is usually used. Aromatic diamines useful in the process of the invention are well known to those skilled in the art. 122330.doc 15 200906910 Examples a (but not limited to this) may be selected from the group consisting of 4,4, oxidized diphenylamine (ODA), p-phenylenediamine (pPDA), m-dimethyl-p-diamine Biphenyl (DMDB), m-bis(trifluoromethyl)-p-diaminobiphenyl, o-dimethyl-monoaminobiphenyl (〇TLD), 4,4,-octafluorobenzidine (〇FB) , tetrafluoro-p-phenylamine (TFPD), 2,2·_5,5,_tetrachlorobenzidine (tcb), 3,3·dichlorobenzidine (DCB), 2,2,-double ( 3-aminophenyl)hexafluoropropane, 2,2,-bis(4-aminophenyl)hexafluoropropane, 4,4,-oxy-bis[3·(trifluoromethyl)aniline, 3' 5 A private base of 3,5-diaminobenzotrifluoride, tetrafluorophenylene diamine, tetrafluoro-m-phenylene diamine, 1,4-double (4- Aminophenoxy)_2_t-butylbenzene (batb), 2,2'-dimethyl-4,4'-bis(4-aminophenoxy)biphenyl (DBAPB), 2,2 - bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (BAPPH), 2,2,-bis[4-(4-aminophenoxy)phenyl]-formane ( BAPN), 5-amino-1-(4,-aminophenyl)-1,3,3-trimethyl Full, 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindan, 4,4'-fluorenylene bis(o-chloroaniline), 3,3 ·-Diphenyldiphenylamine, 3,3'-sulfonyldiphenylamine, 4,4'-diaminobenzophenone, 1,5-diaminonaphthalene, bis(4-aminophenyl) Ethyl decane, bis(4-aminophenyl)diphenyl decane, bis(4-aminophenyl)ethylphosphine oxide, N-(bis(4-aminophenyl))-N- Amine, N-(bis(4-aminophenyl))-N-phenylamine, 4,4'-methylenebis(2-methylaniline), 4,4'-methylenebis ( 2-methoxyaniline), 5,5'-fluorenylene bis(2-aminophenol), 4,4'-methylenebis(2·nonylaniline), 4,4'-oxyl double (2-methoxyaniline), 4,4'-oxybis(2-aniline), 2,2'-bis(4-aminophenol), 5,5,-oxybis(2-amine Phenol), 4,4'-thiobis(2-methylaniline), 4,4,-thiobis(2-decyloxyaniline), 4,4'-thiobis(2-p-benzene) 122330.doc -16· 200906910 Amine), 4,4'-sulfonylbis(2-mercaptoaniline), 4,4'-sulfonylbis(2-ethoxyaniline), 4,4'- Sulfonyl bis(2-chlorobenzene ), 5,5|-sulfonyl bis(2-aminophenol), 3,3f-dimethyl-4,4'-diaminobenzophenone, 3,3'-dimethoxy- 4,4'-diaminobenzophenone, 3,3f-dichloro-4,4'-diaminodibenzophenone, 4,4'-diaminobiphenyl, m-phenylenediamine, 4,4'-methylenediphenylamine (MDA), 4,4'-thiodiamine, 4,4, aryl, amine, 4,4'-isopropylidene diphenylamine, 3, 3'-dimethoxybenzidine, 3,3'-dicarboxybenzidine, 2,4-nonylphenyldiamine, 2,5-tolyldiamine, 2,6-nonylphenyldiamine, between - xylylene diamine, 2,4-diamino-5-methane toluene, 2,4-diaminochlorotoluene, and combinations thereof. Preferably, 4,4,-diphenylamine (〇DA), p-phenylenediamine (pPDA), m-dimethyl-p-diaminobiphenyl (Dmdb), and di-trifluoromethane are used.

甲基二苯胺（MDA)或其混合物。Methyl diphenylamine (MDA) or a mixture thereof.

以下群組之二胺：The following groups of diamines:

122330.doc -17- 200906910 如前述，可視需要於步驟（c)中添加帶有可感光聚合基團 之單體，使所得醯胺酸醋s聚物帶有可感光聚合之基團。 具體言之，於未添加帶有可感光聚合基團之單體時，所 • 得式（1)醯胺酸酯寡聚物中之1為11;而於添加帶有可感光 • 聚合基團之單體時，則所得之式（1)聚醯胺酸前驅物中之Rx 便為該可感光聚合之基團。若Rx為可感光聚合基團，所得 醯胺酸酯寡聚物於後續合成聚醯亞胺樹脂製程中，能產生 ^、 分子與分子間的化學接合而形成交鏈（crosslinking)。 本發明另長:供一種用於製備聚醯亞胺之前驅物組合物， 其係包含前述式（1)之醯胺酸酯募聚物和溶劑。 於本發明組合物中，所使用之溶劑，較佳係為一極性的 非質子性溶劑。舉例言之（但不以此為限），該非質子性溶 劑可選自由以下所組成之群：N-甲基〇比u各酮（nmp)、二 甲基乙醯胺（DMAC)、二甲基甲醯胺（DMF)、二曱基亞砜 (DMSO)、甲苯（toluene)、二曱苯（Xylene)及其混合物。 Q 於本發明前驅物組合物中，以整體組合物之總重量計， 該醯胺酸酯寡聚物之含量為丨5%至70%，較佳為3〇%至 60% ;該溶劑之含量為2〇%至8〇%，較佳為45%至75%。 本發明組合物可視需要包含熟悉此項技術者已知之添加 劑’例如光起始劑、矽烷偶合劑、整平劑、安定劑、催化 - 劑及/或消泡劑等。 當前述式（1)之醯胺酸酯募聚物帶有可感光聚合之基團 時，可視需要添加光起始劑。適用於本發明之光起始劑並 無特殊限制，其可選自以下所組成之群：二苯甲酮 I22330.doc • 18· 200906910 (benzophenone)，二苯乙醇銅（benzoin)、2-經基-2-曱基-1-苯丙酉同（2-hydroxy-2-methyl-l-phenyl-propan- 1-one)、2,2-二甲氧基-1,2-二苯基乙-1- _ (2,2-dimethoxy-l,2- * diphenylethan-1-one)、1_ 羥基環已基苯基酮（1-hydroxy • cycl〇hexyl phenyl ketone)、2,4,6-三曱基苯甲醯基二笨基 膦氧化物（2,4,6-trimethylbenzoyl diphenyl phosphine oxide)、N-苯基甘胺酸、9-苯基吖啶（9-phenylacridine)、 本甲基二甲基縮酮（benzyldimethylketal)、4,4'-雙（二乙基 胺）二苯酮、2,4,5-三芳基咪唑二聚物（2,4,5_ tnarylimidazole dimers)及其混合物；較佳之光起始劑係二 苯甲酮。具體而言，以本發明前驅物組合物之總重量計， 所用光起始劑之含量為〇 〇1至2〇重量％，較佳為〇1至5重 量％。 常用的矽烷偶合劑選自（但不限於）由以下所組成之群： 3-胺丙基三甲氧基矽烷、3_胺丙基三乙氧基矽烷、胺丙 〇 基一甲氧基石夕烧、2_胺丙基三乙氧烧基石夕燒及其混合物。 本發明亦提供一種聚醯亞胺，其係藉由前述式（！）之聚 酿胺酸前驅物聚合而得。舉例言之（但不以此為限），本發 明之聚酿亞胺可藉以下流程圖所示聚合方法而製得： 122330.doc -19· 200906910122330.doc -17- 200906910 As described above, a monomer having a photopolymerizable group may be added in the step (c) as needed to impart a photopolymerizable group to the resulting lysine s s. Specifically, when a monomer having a photopolymerizable group is not added, 1 in the phthalate oligomer of the formula (1) is 11; and a photopolymerizable group is added thereto. In the case of a monomer, Rx in the resulting poly(proline) precursor of formula (1) is the photopolymerizable group. If Rx is a photopolymerizable group, the resulting phthalate oligomer can produce a chemical bond between the molecule and the molecule to form a crosslink in the subsequent synthesis of the polyimide resin. The present invention is further advantageous in that it is used in the preparation of a polyimide precursor composition comprising the phthalate copolymer of the above formula (1) and a solvent. The solvent to be used in the composition of the present invention is preferably a polar aprotic solvent. By way of example (but not by way of limitation), the aprotic solvent may be selected from the group consisting of N-methyl oxime ketone (nmp), dimethyl acetamide (DMAC), dimethyl Methylguanamine (DMF), dimercaptosulfoxide (DMSO), toluene, Xylene, and mixtures thereof. Q In the precursor composition of the present invention, the content of the glutamate oligomer is from 5% to 70%, preferably from 3% to 60%, based on the total weight of the whole composition; The content is from 2% to 8%, preferably from 45% to 75%. The compositions of the present invention may optionally contain additives known to those skilled in the art such as photoinitiators, decane coupling agents, leveling agents, stabilizers, catalyzers and/or defoamers, and the like. When the glutamate conjugate of the above formula (1) has a photopolymerizable group, a photoinitiator may be added as needed. The photoinitiator suitable for use in the present invention is not particularly limited and may be selected from the group consisting of benzophenone I22330.doc • 18·200906910 (benzophenone), benzoin, 2-jing 2-hydroxy-2-methyl-l-phenyl-propan- 1-one, 2,2-dimethoxy-1,2-diphenyl -1- _ (2,2-dimethoxy-l,2- * diphenylethan-1-one), 1-hydroxy • cycl〇hexyl phenyl ketone, 2, 4, 6-three 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, N-phenylglycine, 9-phenylacridine, methyl methacrylate Benzyl dimethylketal, 4,4'-bis(diethylamine) benzophenone, 2,4,5-triarylimidazole dimers (2,4,5-tnarylimidazole dimers) and mixtures thereof; preferably The photoinitiator is benzophenone. Specifically, the photoinitiator is used in an amount of from 1 to 2% by weight, based on the total weight of the precursor composition of the present invention, preferably from 1 to 5% by weight. A commonly used decane coupling agent is selected from, but not limited to, a group consisting of 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and amine propyl thiol-methoxy sulphur 2-Aminopropyltriethoxy burnt stone and its mixture. The present invention also provides a polyimine which is obtained by polymerizing a polyamic acid precursor of the above formula (!). By way of example and not limitation, the polyimine of the present invention can be prepared by the polymerization method shown in the following scheme: 122330.doc -19· 200906910

122330.doc 20· 200906910122330.doc 20· 200906910

N—P-- 傳統聚酿亞胺之合成方法’需先合成大分子量的聚醯胺 酸當作前驅物，但由於分子量過高，黏度太大，以致於操 作性變差，易於塗佈時產生流平性不良等缺點。此外，過 高之聚醯胺酸分子量，當前驅物酿亞胺化時，因分子間之 交互作用以及分子鏈鍵長的縮短，產生極大内應力，致使 所塗佈之基材薄膜麵曲變形。另外，習知聚醯亞胺合成方 法中’其聚合反應形成聚酿胺酸時的固含量，約介於1 〇 % 至3 0%之間，所以經環化後體積收縮比（shrinkage mi()) 大’需多次塗佈方可達到產品要求的厚度，增加製程複雜 度。 本發明之醯胺酸酯寡聚物，其特徵為同時具有酯基（_ C(0)OR及叛基（-C(0)0H)之端基，處於介穩狀態（邮⑷ stable status)，因此在室溫下並不會與自身之胺基（ — Η#) 產生反應’但由於^^酿胺酸則驅物分子量低，因此操控性 佳’塗佈可達到平整效果。在最後固化（post cure)時，升 溫至100C以上，胺基可先將酯基及羧基端基還原成酸 酐’然後再反應成醯胺酸酯寡聚物，之後所得寡聚物進一 步聚合成更大的分子，進而縮合提供具優異熱性質、機械 性質及拉伸性質之聚醯亞胺。相較於習知技術所使用之黏 122330.doc •21 · 200906910 度較大的高分子聚醯胺酸，本發明係使用黏度較小之醯胺 酉夂酉曰寡聚物作為前驅物，故於塗饰時，可里現較高流平性 與操作性。 - 《本發明亞胺之另一特徵在於，由於所使用之前驅物 . 、’且σ物在進行醯亞胺化時，所含之醯胺酸酯寡聚物先進行 分子内環化作用’再進行分子間的聚合與環化作用，可有 效降低聚醯亞胺的殘存之内應力。與習知技術相較，藉由 〇 本發明之前驅物組合物所環化而得之聚醯亞胺，具有不輕 曲的優點。 本發明之聚醯亞胺，由於其前驅物組合物具有高固含量 (high S〇lids c〇ntent)’含有較少溶劑，故可縮短軟烤時間 與降低軟烤溫度，減少因大量溶劑揮發所造成之體積收縮N-P-- Synthesis method of traditional brewing imine' needs to synthesize large molecular weight poly-proline as a precursor, but because the molecular weight is too high, the viscosity is too large, so that the handleability is poor, and it is easy to coat. It has the disadvantages of poor leveling. In addition, the molecular weight of poly-proline is too high, and when the current immigrant is imidized, due to the interaction between molecules and the shortening of the molecular chain bond length, a great internal stress is generated, resulting in a distortion of the coated substrate film. . In addition, in the conventional polyimine synthesis method, the solid content of the polymerization reaction to form poly-brenic acid is between about 1% and 30%, so the volume shrinkage ratio after ringing (shrinkage mi()) Large 'multiple coatings are required to achieve the required thickness of the product, increasing process complexity. The phthalate oligomer of the present invention is characterized in that it has an ester group (_C(0)OR and a thiol (-C(0)0H) end group, and is in a metastable state (mail (4) stable status) Therefore, it does not react with its own amine group (—Η#) at room temperature. 'But because of the low molecular weight of the amine acid, the handleability is good. The coating can achieve a leveling effect. (post cure), when the temperature is raised to 100 C or more, the amine group can first reduce the ester group and the carboxyl end group to an acid anhydride' and then react to form a phthalate oligomer, and then the obtained oligomer is further polymerized into a larger molecule. And condensation to provide a polyimine with excellent thermal, mechanical and tensile properties. Compared with the prior art, the viscosity of 122330.doc • 21 · 200906910 is a large polymer polyamine, this In the invention, the amidoxime oligomer having a small viscosity is used as a precursor, so that higher leveling property and workability can be achieved when coating. - Another feature of the imine of the present invention is that Before using the precursors, 'and the sulphate contains valerate oligos in the imidization The polymer undergoes intramolecular cyclization first, followed by intermolecular polymerization and cyclization, which can effectively reduce the residual internal stress of the polyimine. Compared with the prior art, the precursor combination of the present invention The polyimine obtained by cyclization of the substance has the advantage of not being slight. The polyimine of the present invention has a high solid content (high S〇lids c〇ntent) containing less Solvent, so it can shorten the soft baking time and reduce the soft baking temperature, reduce the volume shrinkage caused by the evaporation of a large amount of solvent

見象並具有乾燥成臈速度快和減少為達産品要求 需的上膠次數等優點。 X 面以往製備聚醢亞胺所需的環化溫度通常高達 〇 c至350 c，然而本發明前驅物組合物於約至 C的皿度下即可進行環化反應，更可降低操作成本。 再者於般间分子聚合都會添加一些單體或短鏈寡聚 體，使分子與分子間能形成交鏈（crosslinking)，然而，本 #明前驅物因含有可感光聚合基團，進而於固化時可自身 交：因此本發明前驅物組合物可以無需包含額外的不飽 ί單體或寡聚體’顯著降低製程複雜度與製程成本。 以下實例將用來例舉本發明之實施態樣，以及Μ釋本發 明之技術特徵，並非用步[jp生丨 卫非用來限制本發明之保護範疇。任何熟 I22330.doc •22- 200906910 悉此技術者可輕易完成之改變咬均 明所主張之範圍，本發明之權利…之安排均屬於本發 ^ ,^ w保護範圍應以所附之申杜 專利範圍為準。 r町之甲。月 實例 以下實施例1至20係例 教侑本發明用於形成聚醯亞胺 之組合物之製作步驟與條件，比 干比較例〗則關於習知技術所 裝侍之用於形成聚醯亞胺之組合物。Seeing and having the advantages of quick drying and reducing the number of times required to meet the product requirements. The cyclization temperature required for the preparation of polyimine from the X surface is usually as high as 〇 c to 350 c, whereas the precursor composition of the present invention can be subjected to a cyclization reaction at a degree of about C to lower the operating cost. Furthermore, in the inter-molecular polymerization, some monomers or short-chain oligomers are added to form a crosslink between the molecules and the molecules. However, the precursor of the present invention contains a photopolymerizable group and is cured. It can be self-crossing: therefore, the precursor composition of the present invention can significantly reduce process complexity and process cost without the need to include additional unsaturated monomers or oligomers. The following examples are intended to illustrate the embodiments of the present invention and to explain the technical features of the present invention, and are not intended to limit the scope of protection of the present invention. Anyone who is familiar with this technology can easily complete the change of the scope claimed by the company. The rights of the present invention are all in accordance with the scope of this issue. The scope of protection should be attached to the application. The scope of the patent shall prevail. A town of R. Examples of Examples The following examples 1 to 20 teach the steps and conditions for the preparation of the composition for forming a polyimide, and the comparative examples are used to form a polyphthalate. A composition of an amine.

Ο 實施例1 將21.81克（0.1莫耳）之均苯 _ .不四駿—酐（pyr〇me丨丨丨以 dianhydride，下文簡稱為PMDA)溶於2〇〇克之队甲基吡咯 烷酮（N-methyl-2-pyrrolidone;下文簡稱為雇卩）中，加熱 所得混合物至5G°C且反應攪拌兩個小時。慢慢滴入i i6、’j 克（0.01莫耳）之丙烯酸2_羥基乙酯（21ι_〇χ^¥ acrylate，下文簡稱為HEA)，於5(rc之固定溫度下反應攪 拌兩個小時。其後，將20.024克（〇_1莫耳）之4,4，_氧化二苯 胺（4,4’-oxydianiline，下文簡稱為0DA)加至溶液中，待 完全溶解後，再於50°C之固定温度下反應攪拌六個小時。 比較例1 將20.024克（0.1莫耳）之〇DA溶於200克之NMP中，冰浴 至〇°C且反應擾拌一個小時，其後加入0.29克（0.002莫耳） 之鄰苯二甲酐（phthalic anhydride)，待反應擾拌一小時 後，再慢慢加入21.59克（0.099莫耳）之？厘0人，於50。(：之 固定溫度下反應攪拌十二個小時。 實施例2 122330.doc -23- 200906910 將21.81克（0.1莫耳）之Pmda溶於200克之NMP中，加熱 至50 C且反應攪拌兩個小時。慢慢滴入13·〇丨克（〇 〇 1莫耳） 之甲基丙烯酸2-經基乙g旨（2_hydroxyethyl methacrylate ;下 - 文簡稱為HEMA)，於50°C之固定溫度下反應攪拌兩個小 - 時。再將20·024克（〇·1莫耳）之ODA加至溶液中，待完全溶 解後’再於50°C之固定溫度下反應攪拌六個小時。 實施例3 f 將21·81克（0.1莫耳）之PMDA溶於200克之NMP中，加熱 至5 0°C且反應攪拌兩個小時。慢慢滴入1」6丨克（〇 〇 1莫耳） 之HEA ’於50°C之固定溫度下反應攪拌兩個小時。再將 10.814 克（0.1 莫耳）之對苯二胺（par<3_phenyienediamine，下 文簡稱為/?PDA)加至溶液中，待完全溶解後，再於5〇。〇之 固定溫度下反應攪拌六個小時。 實施例4 將21.81克（0.1莫耳）之pmdA溶於200克之NMP中，加熱 (j 至50°c且反應攪拌兩個小時。慢慢滴入13.01克（0.01莫耳） 之HEMA，於50°C之固定溫度下反應攪拌兩個小時。再 將10.814克（0.1莫耳）之pPDA加至溶液中，待完全溶解後， 再於50°C之固定溫度下反應攪拌六個小時。 實施例5 將21.81克（〇·1莫耳）之pMDA溶於200克之NMP中，加熱 至5 0 °C下反應攪拌兩個小時。慢慢滴入1 · 161克（0·01莫耳） 之HEA ’於50°C之固定溫度下反應攪拌兩個小時。再將 21.23克（〇.1莫耳）之間二甲基對二胺基聯苯（2,2_(1111^1^1_ 122330.doc -24- 200906910 4,4-diamino-biphenyl ’下文簡稱為DMDB)加至溶液中， 待完全溶解後’再於50。(：之固定溫度下反應攪拌六個小 時。 實施例6 將21.81克（0.1莫耳）之？]^;0入溶於2〇〇克之]^1>中，加熱 至50 C且反應授拌兩個小時。慢慢滴入i 3 .〇丨克（〇 〇 }莫耳） 之HEMA，於50°C之固定溫度下反應攪拌兩個小時。再 將21.23克（0.1莫耳）之DMDB加至溶液中，待完全溶解後， 再於50°C之固定溫度下反應攪拌六個小時。 實施例7 將21.81克（0.1莫耳）之pmdA溶於200克之NMP中，加熱 至5 0 C且反應授拌兩個小時。慢慢滴入】·丨61克（〇_〇 i莫耳） 之HEA，於50°C之固定溫度下反應攪拌兩個小時。再將 21.23克（0.1莫耳）之鄰二甲基對二胺基聯苯（〇_丁〇1池1^;下 文簡稱為〇TLD)加至溶液中，待完全溶解後，再於5〇它 之固定溫度下反應授拌六個小時。 實施例8 將21.81克（0.1莫耳）之？^11)八溶於2〇〇克之>|]^1)中，加熱 至50 C且反應攪拌兩個小時。慢慢滴入13 〇1克（〇 〇1莫耳） 之HEMA，於50°C之固定溫度下反應攪拌兩個小時。再 將21.23克（0.1莫耳）i〇TLD加至溶液中，待完全溶解 後，再於50°C之固定溫度下反應攪拌六個小時。 實施例9 122330.doc -25- 200906910 將21.81克（0.1莫耳）之PMDA溶於200克之NMP中，加熱 至50°C且反應攪拌兩個小時。慢慢滴入1.1 61克（0·01莫耳） 之HEA，於50 °C之固定溫度下反應攪拌兩個小時。再將 32.02克（0.1莫耳）之間二（三氟甲基）對二胺基聯苯（2,2，-bis(trifluoromethyl) benzidine，下文簡稱為 TFMB)加至溶 液中，待完全溶解後，再於50°C之固定溫度下反應攪拌六 個小時。 實施例10 將21.81克（〇·1莫耳）之PMDA溶於200克之NMP中，加熱 至50°C且反應攪拌兩個小時。慢慢滴入13.01克（〇.〇1莫耳） 之HEMA，於50°C之固定溫度下反應攪拌兩個小時。再將 3 2.02克（0.1莫耳）之TFMB加至溶液中，待完全溶解後，再 於50°C之固定溫度下反應攪拌六個小時。 實施例11 將21.81克（0.1莫耳）之PMDA溶於200克之NMP中，加熱 至50 °C且反應授拌兩個小時。慢慢滴入〇·32克（〇_〇1莫耳） 之甲醇，於50°C之固定溫度下反應攪拌兩個小時。再將 20.024克（0.1莫耳）之ODA加至溶液中，待完全溶解後，再 於50 °C之固定溫度下反應攪拌六個小時。 實施例12 將21.81克（〇·1莫耳）之PMDA溶於200克之NMP中，加熱 至5 0 C且反應搜拌兩個小時。慢慢滴入〇. 6 〇 1克（〇. 〇 1莫耳） 之異丙醇’於50C之固定溫度下反應攪拌兩個小時。再將 122330.doc -26- 200906910 20.024克（0.1莫耳）之0DA加至溶液中，待完全溶解後，再 於50°C之固定溫度下反應攪拌六個小時。 實施例13 將21.81克（0.1莫耳）之1>河1^溶於2〇〇克之：^1^1>中，加熱 - 至5〇°C且反應攪拌兩個小時。慢慢滴入0.32克（〇.〇1莫耳） 之曱醇，於50°C之固定溫度下反應攪拌兩個小時。再將 HK814克（0·1莫耳）之户印八加至溶液中，待完全溶解後，再 (‘、 於5 0 C之固定溫度下反應攪拌六個小時。 實施例14 將21.81克（0.1莫耳）之PMDA溶於2〇〇克之ΝΜρ中加熱 至50 C且反應攪拌兩個小時。慢慢滴入〇 6〇1克（〇 〇1莫耳） 之異丙醇，於50。(：之固定溫度下反應攪拌兩個小時。再將 10.814克（0.1莫耳）2pPDA加至溶液中，待完全溶解後，再 於5 0 C之固定溫度下反應攪拌六個小時。 實施例15 Ο 將21.81克（0·1莫耳）之PMDA溶於200克之NMP中，加熱 至50 C下反應攪拌兩個小時。慢慢滴入1〇 32克（〇 〇1莫耳） 之甲醇，於50°C之固定溫度下反應攪拌兩個小時。再將 2 1.23克（0.1莫耳）之DMDB加至溶液中，待完全溶解後，再 於5 0 C之固定溫度下反應攪拌六個小時。 實施例16 將21.81克（0·1莫耳）之PMDA溶於200克之NMP中，加熱 至50 C且反應攪拌兩個小時。慢慢滴入〇 6〇1克（〇 〇1莫耳） 之異丙醇，於50。(：之固定溫度下反應攪拌兩個小時。再將 122330.doc -27- 200906910 21.23克（0.1莫耳）之DMDB加至溶液中，待完全溶解後， 再於50°C之固定溫度下反應攪拌六個小時。 實施例17 將21.81克（0.1莫耳）之PMDA溶於200克之NMP中，加熱 至50 C且反應攪拌兩個小時。慢慢滴入0.32克（0.01莫耳） 之甲醇，於50〇C之固定溫度下反應攪拌兩個小時。再將 21.23克（0.1莫耳）加至溶液中，待完全溶解後， p 再於50°C之固定溫度下反應攪拌六個小時。 實施例18 將21.81克（〇.1莫耳）之？]^1)八溶於2〇〇克之>^1>中，加熱 至50 C且反應攪拌兩個小時。慢慢滴入0.601克（〇.〇丨莫耳） 之異丙醇’於5 0 C之固定溫度下反應攪拌兩個小時。再將 21.23克（0.1莫耳）之0几0加至溶液中，待完全溶解後，再 於50°C之固定溫度下反應攪拌六個小時。 實施例19 Q 將21·81克（0·1莫耳）之PMDA溶於200克之NMP中，加熱 至5 0 C且反應攪拌兩個小時。慢慢滴入〇 ·32克（〇·〇 1莫耳） 之曱醇，於50 t之固定溫度下反應攪拌兩個小時。再將 32.02克（0.1莫耳）之tfMB加至溶液中，待完全溶解後，再 於50°C之固定溫度下反應攪拌六個小時。 實施例20 將21.81克（〇.1莫耳）之PMDA溶於200克之NMP中，加熱 至50°C且反應攪拌兩個小時。慢慢滴入〇 6〇1克（〇 〇ι莫耳） 之異丙醇’於5 0 °C之固定溫度下反應授拌兩個小時。再將 122330.doc -28- 200906910 32.02克（〇.丨莫耳）之TFMB加至溶液中，待完全溶解後再 於50°C之固定溫度下反應攪拌六個小時。 聚醯亞胺物性測試 首先利用Waters Model:201〇的儀器測量所得 聚醯胺酸的分子量相關數據，如下表丨所示： 表1 試品 Mn Mw MP⑴ pD(2) 本發明 (實施例1) 16,129 23,530 21,238 1.458866 習知技術 (比較例1) 106,828 263,324 266,462 2.464926 (1) 峰值分子量 (2) 聚合物分散性（polydispersity) 由表1數據可知，本發明方法可提供具較低聚合物分散 性之聚醯胺酸，亦即所製得聚醯胺酸之分子量範圍分布較 窄、高低分子量差距較小，其品質較佳。 取實施例1與比較例1所得組合物以旋轉塗佈之方式製作 薄膜。再進一步以烘箱烘烤，而升溫曲線分為三段，分別 為 150。(：/60 min，25(TC/60 min 及 35(rc/12〇 min，其升溫 速度為2°C/min，之後，冷卻回溫。進行物性測試。 接著，利用萬能拉力機（宏達出產的高溫彎曲測定儀 Mode! 9102)進行聚醯亞胺膜機械性質之測試。將所得聚 酿亞胺膜裁切成12 cmxlO cmx0.25 mm之大小，架置於， 萬能拉力機上，於溫度23 t下進行，速度設定為= 122330.doc -29- 200906910 mm/min，分別對由實施例丨組合物及比較例丨組合物所得 聚醯亞胺膜作拉力測試，以量測不同之抗張強度，結果如 表2所示： 表2 試品 拉抗強度 (MPa) 伸長長度百分比 (%) 本發明 (實施例1) 78.896 11.185 % 習知技術 (比較例1) 74.3 5.415 % 由表2結果顯示，本發明所提供之聚醯亞胺膜，可展現 較為優異之拉伸強度與伸長率。 122330.doc 30-实施 Example 1 21.81 g (0.1 mol) of benzene _. 四 骏 — 酐 酐 py dian dian dian dian dian dian dian dian dian dian dian dian dian dian ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Methyl-2-pyrrolidone; hereinafter referred to as "employed"), the resulting mixture was heated to 5 G ° C and stirred for two hours. Slowly drip i i6, 'j g (0.01 mol) of 2-hydroxyethyl acrylate (21ι_〇χ^¥ acrylate, hereinafter referred to as HEA), and stir for two hours at a fixed temperature of 5 (rc). Thereafter, 20.024 g of 4,4'-oxydianiline (hereinafter referred to as 0DA) is added to the solution, and after completely dissolved, it is further 50°. The reaction was stirred for six hours at a fixed temperature of C. Comparative Example 1 20.024 g (0.1 mol) of hydrazine DA was dissolved in 200 g of NMP, ice-cooled to 〇 ° C and the reaction was scrambled for one hour, after which 0.29 g was added. (0.002 mol) of phthalic anhydride, after the reaction was stirred for one hour, slowly add 21.59 g (0.099 mol) of PCT to 50. (: at a fixed temperature The reaction was stirred for twelve hours. Example 2 122330.doc -23- 200906910 21.81 g (0.1 mol) of Pmda was dissolved in 200 g of NMP, heated to 50 C and stirred for two hours. · 〇丨克(〇〇1莫耳) methacrylic acid 2- via 2-ethylethyl methacrylate; The reaction was stirred at a fixed temperature of 50 ° C for two hours, then 20.024 g (〇·1 mol) of ODA was added to the solution, and after completely dissolved, 'react at a fixed temperature of 50 ° C. Stir for six hours.Example 3 f Dissolve 21·81 g (0.1 mol) of PMDA in 200 g of NMP, heat to 50 ° C and stir for two hours. Slowly drip 1" 6 g (〇〇1 Moel) HEA 'The reaction was stirred for two hours at a fixed temperature of 50 ° C. Then 10.814 g (0.1 mol) of p-phenylenediamine (par < 3_phenyienediamine, hereinafter referred to as /? PDA) Add to the solution, after completely dissolved, and stir for 6 hours at a fixed temperature of 5 Torr. Example 4 21.81 g (0.1 mol) of pmdA was dissolved in 200 g of NMP and heated (j to The reaction was stirred for two hours at 50 ° C. 13.01 g (0.01 mol) of HEMA was slowly added dropwise, and the reaction was stirred for two hours at a fixed temperature of 50 ° C. Then 10.814 g (0.1 mol) of pPDA was added. To the solution, after completely dissolved, the reaction was stirred for six hours at a fixed temperature of 50 ° C. Example 5 21.81 g (〇· 1 mol) pMDA is dissolved in 200 g of NMP, heated to 50 ° C and stirred for two hours. Slowly drip 1 · 161 g (0. 01 mol) of HEA ' fixed at 50 ° C The reaction was stirred at temperature for two hours. Further, 21.23 g (〇.1 mol) of dimethyl-p-diaminobiphenyl (2,2_(1111^1^1_122330.doc -24-200906910 4,4-diamino-biphenyl ' hereinafter referred to as DMDB) was added to the solution, and after being completely dissolved, 'further at 50. (: The reaction was stirred for six hours at a fixed temperature. Example 6: 21.81 g (0.1 mol) of ?? In the case of 〇克之^^>, heat to 50 C and allow the reaction to stir for two hours. Slowly drip the HEMA of i 3 gram (〇〇}mole) and stir at a fixed temperature of 50 °C. Two hours. 21.23 grams (0.1 mole) of DMDB was added to the solution. After complete dissolution, the reaction was stirred for six hours at a fixed temperature of 50 ° C. Example 7 21.81 g (0.1 mol) The pmdA is dissolved in 200g of NMP, heated to 50 C and reacted for two hours. Slowly drip into the HEA of 61 g (〇_〇i Moer) at a fixed temperature of 50 °C. The reaction was stirred for two hours, and 21.23 g (0.1 mol) of o-dimethyl-p-diaminobiphenyl (〇_丁〇1池; hereinafter referred to as 〇TLD) was added to the solution, to be completely After dissolving, then 5 The reaction was stirred for six hours at its fixed temperature. Example 8 21.81 g (0.1 mol) of ?11) was dissolved in 2 g of >|]^1) and heated to 50 C and The reaction was stirred for two hours. Slowly add 13 〇 1 g (〇 莫 1 mol) of HEMA and stir at a fixed temperature of 50 ° C for two hours. Further, 21.23 g (0.1 mol) of i〇TLD was added to the solution, and after completely dissolved, the reaction was stirred at a fixed temperature of 50 ° C for six hours. Example 9 122330.doc -25- 200906910 21.81 g (0.1 mol) of PMDA was dissolved in 200 g of NMP, heated to 50 ° C and stirred for two hours. 1.1 F (0.101 mol) of HEA was slowly added dropwise, and the reaction was stirred at a fixed temperature of 50 ° C for two hours. Further, 32.02 g (0.1 mol) of bis(trifluoromethyl)-p-diphenylbiphenyl (2,2,-bis(trifluoromethyl) benzidine, hereinafter referred to as TFMB) was added to the solution, after being completely dissolved. The reaction was further stirred at a fixed temperature of 50 ° C for six hours. Example 10 21.81 g (〇·1 mol) of PMDA was dissolved in 200 g of NMP, heated to 50 ° C and stirred for two hours. The HEMA of 13.01 g (〇.〇1 mol) was slowly added dropwise, and the reaction was stirred at a fixed temperature of 50 ° C for two hours. Further, 3 2.02 g (0.1 mol) of TFMB was added to the solution, and after completely dissolved, the reaction was stirred at a fixed temperature of 50 ° C for six hours. Example 11 21.81 g (0.1 mol) of PMDA was dissolved in 200 g of NMP, heated to 50 ° C and reacted for two hours. The methanol of 〇·32 g (〇_〇1 mol) was slowly added dropwise, and the mixture was stirred at a fixed temperature of 50 ° C for two hours. Further, 20.024 g (0.1 mol) of ODA was added to the solution, and after completely dissolved, the reaction was stirred at a fixed temperature of 50 ° C for six hours. Example 12 21.81 g (〇·1 mol) of PMDA was dissolved in 200 g of NMP, heated to 50 C and allowed to mix for two hours. Slowly drip in. 6 〇 1 g (〇. 〇 1 mol) of isopropanol' was stirred at a fixed temperature of 50 C for two hours. Further, 122330.doc -26-200906910 20.024 g (0.1 mol) of 0DA was added to the solution, and after completely dissolved, the reaction was stirred at a fixed temperature of 50 ° C for six hours. Example 13 21.81 g (0.1 mol) of 1>River 1 was dissolved in 2 g of: ^1^1>, heated to 5 ° C and stirred for two hours. 0.32 g of sterol was slowly added dropwise, and the mixture was stirred at a fixed temperature of 50 ° C for two hours. Then add HK814 g (0·1 mol) to the solution, and after it is completely dissolved, (', stir at a fixed temperature of 50 C for six hours. Example 14 will be 21.81 g ( 0.1 mol of PMDA is dissolved in 2 g of ΝΜρ heated to 50 C and the reaction is stirred for two hours. Slowly add 〇6〇1 g (〇〇1 mol) of isopropanol at 50. The reaction was stirred for two hours at a fixed temperature. Further, 10.814 g (0.1 mol) of 2pPDA was added to the solution, and after completely dissolved, the reaction was stirred for six hours at a fixed temperature of 50 C. Example 15 21.81 g (0.1 mol) of PMDA was dissolved in 200 g of NMP, and the mixture was stirred for 2 hours while heating to 50 C. 1 〇 32 g (〇〇1 mol) of methanol was slowly added dropwise to 50 The reaction was stirred for two hours at a fixed temperature of ° C. Then, 2.23 g (0.1 mol) of DMDB was added to the solution, and after completely dissolved, the reaction was stirred at a fixed temperature of 50 C for six hours. Example 16 21.81 g (0.1 mol) of PMDA was dissolved in 200 g of NMP, heated to 50 C and stirred for two hours. 〇6〇1g (〇〇1mol) of isopropanol, stir at room temperature for 50 hours at a fixed temperature. 122330.doc -27- 200906910 21.23 g (0.1 m) DMDB Add to the solution, and after completely dissolving, stir the reaction for six hours at a fixed temperature of 50 ° C. Example 17 21.81 g (0.1 mol) of PMDA was dissolved in 200 g of NMP and heated to 50 C and The reaction was stirred for two hours. 0.32 g (0.01 mol) of methanol was slowly added dropwise, and the reaction was stirred for two hours at a fixed temperature of 50 ° C. 21.23 g (0.1 mol) was added to the solution until it was completely After dissolution, p was further stirred and reacted for six hours at a fixed temperature of 50 ° C. Example 18 21.81 g (〇.1 mol) of ?]^1) was dissolved in 2 g of >^1> Heat to 50 C and stir for two hours. Slowly add 0.601 g of isopropyl alcohol to the reaction at a fixed temperature of 50 ° C for two hours. Then add 21.23 g. 0 (0 mol) of 0 (0.1 mol) was added to the solution, and after completely dissolved, the reaction was stirred for 6 hours at a fixed temperature of 50 ° C. Example 19 Q Dissolve 21·81 g (0.1 mol) of PMDA in 200 g of NMP, heat to 50 C and stir for two hours. Slowly add 〇·32 g (〇·〇1 mol) The sterol is stirred at a fixed temperature of 50 t for two hours. Then 32.02 g (0.1 mol) of tfMB is added to the solution, and after completely dissolved, the reaction is stirred at a fixed temperature of 50 ° C. Hours. Example 20 21.81 g (〇.1 mol) of PMDA was dissolved in 200 g of NMP, heated to 50 ° C and stirred for two hours. Slowly drip 〇 6 〇 1 g (〇 〇ι Mo) of isopropanol' at a fixed temperature of 50 ° C for two hours. Then, TFMB of 122330.doc -28-200906910 32.02 g (〇.丨莫耳) was added to the solution, and after completely dissolved, the reaction was stirred at a fixed temperature of 50 ° C for six hours. Polyimine physical property test First, the molecular weight related data of the obtained polylysine was measured using a Waters Model: 201 〇 instrument, as shown in the following table: Table 1 Test sample Mn Mw MP (1) pD (2) The present invention (Example 1) 16,129 23,530 21,238 1.458866 Conventional Technology (Comparative Example 1) 106,828 263,324 266,462 2.464926 (1) Peak molecular weight (2) Polymer dispersity As can be seen from the data in Table 1, the method of the present invention can provide a lower polymer dispersibility. Polylysine, that is, the polyglycine produced has a narrow molecular weight range, a small difference in height and low molecular weight, and a better quality. The compositions obtained in Example 1 and Comparative Example 1 were formed into a film by spin coating. Further baked in an oven, and the temperature rise curve is divided into three sections, respectively 150. (:/60 min, 25 (TC/60 min and 35 (rc/12 min, the heating rate is 2 °C/min, after which it is cooled back to temperature. Physical property test. Next, using the universal tension machine (Hongda production) The high temperature bending tester Mode! 9102) tests the mechanical properties of the polyimide film. The obtained polyimide film is cut into 12 cm x 10 cm x 0.25 mm, placed on a universal tensile machine at a temperature. The reaction was carried out at 23 t, and the speed was set to = 122330.doc -29-200906910 mm/min. The tensile tests of the polyimine films obtained from the compositions of the examples and the comparative examples were respectively tested to measure different resistances. Tensile strength, the results are shown in Table 2: Table 2 Tensile tensile strength (MPa) Percent elongation length (%) The present invention (Example 1) 78.896 11.185 % Conventional technique (Comparative Example 1) 74.3 5.415 % From Table 2 The results show that the polyimine film provided by the present invention can exhibit superior tensile strength and elongation. 122330.doc 30-

Claims (1)

200906910 十、申請專利範圍： ^ 一種聚醯亞胺之前驅物，其具下式（1)之結構：200906910 X. Patent application scope: ^ A polyimine precursor, which has the structure of the following formula (1): 其中 R為具1至14個碳原子之直鏈或支鏈烧基、具6至14個碳 原子之芳基或芳烷基或乙烯系不飽和基； RX各自獨立為Η或乙烯系不飽和基； G各自獨立為4價有機基團； P各自獨立為2價有機基團；以及 m係〇至100之整數。 丨哪乳丞丁基、甲基 及具下式（2)之基團 2_如凊求項i之前驅物，其中該乙烯系不飽和基係選自以 下群組·乙烯基、丙浠基、甲基丙烯基、正丁稀基、異 丁烯基'乙烯基苯基、丙烯基苯基、丙烯氧基甲基、丙 稀氧基乙基、丙烯氧基丙基、丙烯氧基丁基、丙烯氧基 戊基、丙烯氧基己基、甲基丙烯氧基甲基、甲基丙烯氧 基乙基、甲基丙烯氧基丙基、甲基丙烯氧基丁基、 丙烯氧基戊基、甲基丙烯氧基己基、Wherein R is a linear or branched alkyl group having 1 to 14 carbon atoms, an aryl or aralkyl group having 6 to 14 carbon atoms or an ethylenically unsaturated group; and each RX is independently hydrazine or ethylenically unsaturated. Each of G is independently a tetravalent organic group; P is each independently a divalent organic group; and m is an integer from 〇 to 100.丞 丞 butyl, methyl and the group of the following formula (2) 2_, such as the precursor of the item i, wherein the ethylenically unsaturated group is selected from the group consisting of vinyl, propyl fluorenyl , methacryl, n-butyl, isobutylene 'vinylphenyl, propenylphenyl, propyleneoxymethyl, propyloxyethyl, propyleneoxypropyl, propyleneoxybutyl, propylene Oxypentyl, propyleneoxyhexyl, methacryloxymethyl, methacryloxyethyl, methacryloxypropyl, methacryloxybutyl, propyleneoxypentyl, methyl Propyleneoxyhexyl, 直鏈或支鏈之C丨-C8 其中Rl為伸苯基、C3_C8伸環烷基、 122330.doc 200906910 伸烷基、d-Cs伸烯基或Ci_C8羥基伸烷基，及r2為氫或 C1-C4貌基。 3.如6月求項1之前驅物，其中rx各自獨立為H、甲基丙烯 酉文-2-羥基丙酯基、甲基丙烯酸乙酯基、丙烯酸乙酯基、 丙烤基、曱基丙稀基、正丁稀基或異丁烯基。 4·如吻求項1之前驅物，其中&amp;各自獨立為Η或甲基丙烯 酸-2_羥基丙酯基。 5.如明求項丨之前驅物，其中該4價有機基團係選自由下列 基團所構成群組：Linear or branched C丨-C8 wherein R1 is phenyl, C3_C8 cycloalkyl, 122330.doc 200906910 alkyl, d-Cs alkenyl or Ci_C8 hydroxyalkyl, and r2 is hydrogen or C1 -C4 appearance. 3. For example, in June, the precursor of the first item, wherein each of rx is independently H, methacryloyl-2-hydroxypropyl ester group, ethyl methacrylate group, ethyl acrylate group, propyl group, fluorenyl group A propylene, n-butyl or isobutenyl group. 4. For example, before the kiss 1 , wherein &amp; each is independently hydrazine or methacrylic acid-2 hydroxypropyl ester group. 5. The precursor of the invention, wherein the tetravalent organic group is selected from the group consisting of: 其中Y各獨立為氫、 及 B 為-CH2-、_〇_ -c(cf3)2_。 鹵素、CVC4全氟烷基或Cr-C4烷基， 、-S-、-CO-、-S〇2-、-C(CH3)2-或 6. 如請求1自 之别驅物’其中該4價有機基團係選自由下列 基團所構成群組：Wherein each Y is independently hydrogen, and B is -CH2-, _〇_-c(cf3)2_. Halogen, CVC4 perfluoroalkyl or Cr-C4 alkyl, -S-, -CO-, -S〇2-, -C(CH3)2- or 6. If requested 1 from the other's The tetravalent organic group is selected from the group consisting of the following groups: 122330.doc122330.doc 及 cf3 如叫求項1之前驅物，其中該2價有機基團係選自由下列 200906910 基團所構成群組：And cf3 are referred to as precursors of claim 1, wherein the divalent organic group is selected from the group consisting of the following 200906910 groups: 其中X各自獨立為風、鹵素、C1-C4烧基或C1-C4全氣院 基，A 為·〇-、-S-、-CO-、-CH]-、-OC(O)-或-CONH-; 以及w及z各自為1至3之整數。 8.如請求項7之前驅物，其中該2價有機基團係選自由下列 基團所構成群組：Wherein X is independently wind, halogen, C1-C4 alkyl or C1-C4 full gas, and A is ·〇-, -S-, -CO-, -CH]-, -OC(O)- or - CONH-; and w and z are each an integer from 1 to 3. 8. The precursor of claim 7, wherein the divalent organic group is selected from the group consisting of: H3CPH3 --CHlsi-O—Si— -CH2— 3 H3(^ tffe 3 9.如請求項1之前驅物，其中m係5至25之整數。 1 0.如請求項1之前驅物，其中R為選自由下列基團所構成群 CH3〇 H2C—C — C— 0— C2H4— 0 II H2C— C—C—〇—C2H4— Η 122330.doc 200906910 CH3〇 H2C=C-c-0-CH2-CH-CH2- OH „ r__l II n2c_ c—〇_ CH2_ ch_ ch2- OHH3CPH3 - CHlsi-O-Si - -CH2 - 3 H3 (^ tffe 3 9. The precursor of claim 1 wherein m is an integer from 5 to 25. 1 0. As claimed in claim 1, where R It is selected from the group consisting of CH3〇H2C—C—C—0—C2H4— 0 II H2C—C—C—〇—C2H4—Η 122330.doc 200906910 CH3〇H2C=Cc-0-CH2-CH- CH2- OH „ r__l II n2c_ c—〇_ CH2_ ch_ ch2- OH ch3Ch3 其中n係〇至10之整數。 11 _ 一種聚醯亞胺之前驅物組合物’其係包含如請求項1之 鈿驅物和溶劑。 12.如請求項丨丨之組合物’其中該溶劑係選自由N_甲基吡哈 _、二甲基乙醯胺、二甲基曱醢胺、二甲基亞硬、甲 苯、二甲苯及其混合物所組成之群組。Where n is an integer from 〇 to 10. 11 _ A polyimine precursor composition&apos; which comprises the oxime drive and solvent of claim 1. 12. The composition of claim </RTI> wherein the solvent is selected from the group consisting of N-methylpyrazine, dimethylacetamide, dimethylamine, dimethyl sulfoxide, toluene, xylene, and a group of mixtures thereof. 13·如請求項丨丨之組合物，進一步包含一光起始劑，該光起 始劑係選自由二苯甲酮、二苯乙醇鋼、2_經基·2_甲基+ 苯丙酮、2 2_二曱氧基4 2_ - —本基乙-1-酮、1_羥基環已 基苯基酮、2,4,6-三甲基苯甲醢 r 基一苯基膦氧化物、沭 苯基甘胺酸、9-苯基吖啶、笨甲萁_ m w 甲基一甲基縮酮、4,4'-雙 聚物及其混合物 (一乙基胺）二苯酮、2,4,5-三 所組成之群組。 求項1之前驅物 而獲 14. 一種聚醯亞胺 得。 其係藉由聚合如請 122330.doc 200906910 七、指定代表圖： (一) 本案指定代表圖為：（無） (二) 本代表圖之元件符號簡單說明： 八、本案若有化學式時，請揭示最能顯示發明特徵的化學式：13. The composition of claim 1, further comprising a photoinitiator selected from the group consisting of benzophenone, diphenylethyl alcohol steel, 2_transyl-2-methyl+propiophenone, 2 2 —dimethoxy 4 2 — —benyl ethyl-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzimid-yl-phenylphosphine oxide, Phenyl phenylglycine, 9-phenyl acridine, benzoate 萁 mw methyl monomethyl ketal, 4, 4 '-dimer and mixtures thereof (monoethylamine) benzophenone, 2, 4,5-three groups. In the first step of the invention, the precursor was obtained. 14. A polyimine was obtained. It is by means of polymerization. Please refer to 122330.doc 200906910. 7. Designation of representative drawings: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 8. If there is a chemical formula in this case, please Reveal the chemical formula that best shows the characteristics of the invention: 122330.doc 200906910 %年&quot;月％ 發明專利說明書 中文說明書替換頁(96年11月） (本說明書格式、順序及粗體字，請勿任意更動，※記號部分請勿填寫） ※申請案號：096128743 ※申請曰期：0./' ; ※”(：分類：C08G〒V^ m. :! 一、 發明名稱：（中文/英文） 聚醯亞胺之前驅物及其應用 PRECURSOR FOR POLYIMIDE AND USE THEREOF 二、 申請人：（共1人） ( 姓名或名稱：（中文/英文） 長興化學工業股份有限公司 ETERNAL CHEMICAL CO., LTD. 代表人：（中文/英文） 高英士 KAO, YING-SHIH 住居所或營業所地址：（中文/英文） 高雄市三民區建工路578號 No. 578, CHIEN KUNG RD., KAOHSIUNG, TAIWAN, R.O.C. 國籍：（中文/英文） 中華民國 TAIWAN，R.O.C. 三、 發明人：（共2人） 姓名：（中文/英文） 1. 吳仲仁 WU, CHUNG-JEN 2. 蔣舜人 CHIANQ SHUN-JEN 國籍：（中文/英文） 1 ·中華民國 TAIWAN, R.O.C. 2.中華民國 TAIWAN，R.O.C. 122330.doc122330.doc 200906910 %Year &quot;Monthly % Inventor Patent Specification Chinese Manual Replacement Page (November, 1996) (Do not change the format, order and bold text of this manual, please do not fill in the ※ part) ※Application number :096128743 ※Application deadline: 0./' ; ※"(:Classification: C08G〒V^ m. :! I. Invention name: (Chinese / English) Polyimine precursor and its application PRECURSOR FOR POLYIMIDE AND USE THEREOF II. Applicant: (1 in total) (Name or Name: (Chinese/English) ETERNAL CHEMICAL CO., LTD. Representative: (Chinese/English) Gao Yingshi KAO, YING-SHIH Address of residence or business office: (Chinese / English) No. 578, Jiangong Road, Sanmin District, Kaohsiung City No. 578, CHIEN KUNG RD., KAOHSIUNG, TAIWAN, ROC Nationality: (Chinese / English) TAIWAN, ROC III, Invention Person: (Total 2 persons) Name: (Chinese / English) 1. Wu Zhongren WU, CHUNG-JEN 2. Jiang Yanren CHIANQ SHUN-JEN Nationality: (Chinese / English) 1 · Republic of China TAIWAN, ROC 2. The Republic of China TAIWAN, R.O.C. 122330.doc
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