TWI376395B

TWI376395B - Water soluble photo-sensitive polyimide polymer, process for preparing the same, and photoresist composition containing the same

Info

Publication number: TWI376395B
Application number: TW97151347A
Authority: TW
Inventors: Jen Fu Wang; Sheng Yen Wu; An Pang Tu; Kuen Yuan Hwang
Original assignee: Chang Chun Plastics Co Ltd
Priority date: 2008-12-30
Filing date: 2008-12-30
Publication date: 2012-11-11
Also published as: TW201024336A; JP5009953B2; JP2010155962A

Description

1376395 六、發明說明：【發明所屬之技術領域】本發明有關一種水溶性感光聚醯亞胺聚合物以及其製法。詳言之，係有關一種對有機溶劑及驗性水溶液具有良好溶解度、於成膜後具有優異耐熱性、繞性以及電絕緣特性之水溶性感光聚醯亞胺聚合物，而可廣泛應用於電子產業。【先前技術】於半導體製程中，有利用光微影银刻技術於基板上進行線路緣製’於該微影蝕刻技術有必要利用到感光性;^丨脂，藉由感光性樹脂對輻射線之感光性，而可在透過具有所需圖案之光罩曝光後’利用驗溶液等洗除曝光部份或未曝光部份，即可獲得具有所需圖案之印刷電路板。 5587275專利案中揭示一種聚醯亞胺前驅物，其具有下述 •示之結構單位：八 f ί Π 在光微影蝕刻技術中所用之感光性樹脂，已多有開發如於US 5587275直剎垒由掘s —括取搞_ . • HOir r ο ο1376395 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a water-soluble photosensitive polyimide pigment polymer and a process for producing the same. In particular, it relates to a water-soluble photosensitive polyimide polymer which has good solubility to organic solvents and aqueous solutions, and has excellent heat resistance, winding properties and electrical insulating properties after film formation, and can be widely used in electronics. industry. [Prior Art] In the semiconductor manufacturing process, the circuit edge is formed on the substrate by photolithography and silver engraving technology. It is necessary to use the photolithography in the lithography etching process; ^Rouge, the radiation is irradiated by the photosensitive resin The photosensitive property can be obtained by washing the exposed portion or the unexposed portion with a test solution or the like after being exposed through a mask having a desired pattern to obtain a printed circuit board having a desired pattern. The 5587275 patent discloses a polyimine precursor having the following structural unit: 八f ί Π Photosensitive resin used in photolithography etching technology has been developed as in US 5587275 The barrier is made by digging s. _. • HOir r ο ο

其中R為虱原子或曱基。Wherein R is a halogen atom or a fluorenyl group.

後，再與四酸二酐單體反 1376395 應，得到上述式(1)之聚醯亞胺前驅物。 ^另於US6025113則揭示具有以下述式早位之聚醯亞胺前驅物：式(4)表示之重複 •①一J1~~CONH—R2. (°〇〇R3)2 inThereafter, it is further reacted with a tetrabasic dianhydride monomer 1376395 to obtain a polyimine precursor of the above formula (1). ^ In addition to US6025113, it is disclosed that the polyimine precursor having the formula: (4) is repeated: • 1 J1~~CONH-R2. (°〇〇R3) 2 in

其中R1為含4或更多碳原子之四價有H 族環之三價細價有機基；R3為 ^含至少-個秀且η為1或2; 、有機基，Α為酸性單價基；〇〇 1一R1—C0 (000113)2 (4) 娜機基； ΐ f基與^醯胺酸間形成醋鍵用 =;，亞_之官能“;=而完成本發明。之光顯影後’再利用高溫環化形成具出具有水溶性之感光性聚丨【發明内容】 .醯亞胺樹脂，而為具=式種水溶性感光聚醯_合物，其特徵Wherein R1 is a trivalent fine-valent organic group having a tetravalent H-group ring having 4 or more carbon atoms; R3 is at least - and η is 1 or 2; and an organic group is an acidic monovalent group; 〇〇1 - R1 - C0 (000113) 2 (4) Naji base; ΐ f base and ^ proline acid form vinegar bond =;, sub-function "; = and completed the invention. After light development 'Reuse of high-temperature cyclization to form a photosensitive polyfluorene having water solubility. [Inventive content] A quinone imine resin, which is a water-soluble photosensitive poly- conjugate having the formula

Γ—s f oa^vho R OA Yoim 3 y ria^ N OA vno R oanyo En 、 2"o N-R/ol?= onu^ VMO Rr OA Yo N ο H3 S3丨 rCH3 1376395Γ—s f oa^vho R OA Yoim 3 y ria^ N OA vno R oanyo En , 2"o N-R/ol?= onu^ VMO Rr OA Yo N ο H3 S3丨 rCH3 1376395

Rg -CRt=cR〇Rg -CRt=cR〇

r9 或R9 or

有4個以上碳原子之四價有機基；&為3價或4 ϋ機基，其上可視情狀帶有絲;R3表示 ttt ^ 3 i至6個碳原子之伸烷基、含6至2〇個 m?基：烷基;…及心可相同或不同且』立:選自a tetravalent organic group having 4 or more carbon atoms; & is a trivalent or 4 fluorene group, which has a filament on a visual condition; R3 represents an alkyl group of ttt ^ 3 i to 6 carbon atoms, and contains 6 to 2〇m? base: alkyl; ... and heart can be the same or different and stand:

原子之齡上====== \及n表7^於或等於1之整數；m及k表示大於〇之整數];且上述各重複單位可為嵌段聚合亦可為隨機聚合。，本發明之水溶性感光聚醯亞胺聚合物藉，轉換成聚苯乙烯計之重量平均/子由量疑膠⑽ =〇〜卿⑻，較佳約為20，_〜150，_，其特性黏度(IV)2 為0.20495’較好為_〜0.85，且其5%熱重損失低於 350°C，較好低於 340。(：。 M cuw/o))The atomic age is ====== \ and n is 7^ at or equal to 1 integer; m and k are integers greater than ]]; and each of the above repeating units may be block polymerization or random polymerization. The water-soluble photosensitive polyimine polymer of the present invention is converted into polystyrene by weight average/sub-quantity (10) = 〇~qing (8), preferably about 20, _~150, _, The intrinsic viscosity (IV) 2 is 0.20495', preferably _~0.85, and its 5% thermogravimetric loss is less than 350 ° C, preferably less than 340. (:. M cuw/o))

本發财，±述特性黏度係將聚合物濃纽料Q ^物溶液’以Ν-甲基轉咬酮卿^)作為溶劑，以毛細管黏声計(Ubbelohode viscometer)測定’再以下述公式計算其固有黏产= 值：、’又 V inh=ln(t/t0)/0.5(g/dl) 重分析儀其中t(H谷劑通過黏度計上下兩刻度的空白組時間(秒） t=聚合物溶液通過黏度計上下兩刻度的時間(秒）。本發明中，上述5%熱分解溫度(1(1(：95〇/(^係使用熱 (TGA)測定之樹脂5%熱分解時之溫度。 … 本發明之水溶性感光性聚醯亞胺聚合物驗性水溶解度優異’於塗佈成膜(膜厚1〇〜25μιη)時，將膜片（尺寸:9*5 5一溶解於looo宅升之iwto/“炭酸鈉水溶液中之溶解時間少於2分 1376395 鐘，顯示具有良好的驗水溶液溶解度。光親本亞製備具有下式①之重複單位之水溶性感This is a fortune, the characteristic viscosity is determined by using a capillary viscometer (Ubbelohode viscometer) as a solvent for the polymer concentration Q ^ solution [using Ν-methyl ketone ketone] and then calculated by the following formula Its intrinsic cohesive yield = value: ', V inh = ln(t / t0) / 0.5 (g / dl) Re-analyzer t (H) through the viscometer up and down two scales of the blank group time (seconds) t = The time (seconds) in which the polymer solution passes through the upper and lower scales of the viscometer. In the present invention, the above 5% thermal decomposition temperature (1 (1: 95 〇 / (^) is determined by thermal decomposition (TGA) of the resin 5% thermal decomposition The temperature of the water-soluble photosensitive polyimine polymer of the present invention is excellent in the water solubility of the coating. When the film is formed into a film (film thickness: 1 〇 to 25 μm), the film (size: 9*5 5 is dissolved) The dissolution time of the iwto/"sodium carbonate aqueous solution in the loo shoji is less than 2 minutes 1376395 minutes, showing good solubility in the aqueous solution. The light parent is prepared to have the water solubility of the repeating unit of the following formula 1.

oa^vnoOA Yo N —c=丨Re—Oa^vnoOA Yo N —c=丨Re—

OA^yno OA Yo NOA^yno OA Yo N

3 y RIA3 y RIA

ΟΛ Vo R OA Yo N oh3jh3 cIs—c Η3/^ν H3 cIsIc cIoΟΛ Vo R OA Yo N oh3jh3 cIs—c Η3/^ν H3 cIsIc cIo

R6= ~~-CR7=CR8 * ίί: ’ Rl為含有4個以上碳原子之四價有機基；&為3價或4 基’其上可視情況又帶有縣表示2價至4價有機基; 人表不0H或COOH基；仏及尺5可相同亦可不同，分別表示為 :1至6個f原子之伸烷基、含ό至20個碳原子之伸芳基、伸，燒基、伸芳氣基伸烷基；R<7及馬可相同或不同且獨立為選自氣、鹵$、幾基、含UO個碳之直鏈或環狀烷基、含6_2〇個碳原子之芳基、烷芳基及芳烷基；R?表示氫原子或含有i至6個碳原子之烷基；X表示1或2之整數；y表示0、丨或2之整數；a、 b及η表示大於或等於1之整數，· m及让表示大於〇之整數]，·其中各重複單為可為嵌段聚合或無規聚合；〃該方法包括下列步驟： (a) ，四幾酸一酐與具有缓基及/或經基官能基之二胺進行反應，獲得主鏈上具有羧基及/或羥基官能基之聚醯胺酸前驅物；其中四幾酸一酐對二胺之莫耳當量比為四羧酸二酐：二工： 0.8〜1 : 1.2。 (b) 使上述(a)所得之主鏈上具有羧基及/或羥基官能基之聚醯胺酸前驅物進行加熱環化，獲得主鏈上具有羧基及/或羥基官能 1376395 聚醯亞胺；及 (二)使上述(b)所得之主鏈上具有羧基及/或羥基官能基之聚醯亞胺中之羥基與下式(Π)之二酸酐進行酸酐之開環反應： Λ Υ ο (Π) (式中，R«= r9 'CR^^CRg-R6= ~~-CR7=CR8 * ίί: ' Rl is a tetravalent organic group containing 4 or more carbon atoms; & is a 3 or 4 base ', and it can be represented by a county with a price of 2 to 4 organic The human surface is not 0H or COOH group; the crucible and the ruler 5 may be the same or different, and are respectively represented by: an alkyl group of 1 to 6 f atoms, an extended aryl group containing fluorene to 20 carbon atoms, and an extension. Alkyl, an extended aromatic alkyl group; R<7 and equine may be the same or different and independently selected from the group consisting of a gas, a halogen, a certain group, a linear or cyclic alkyl group containing UO carbons, and having 6 to 2 carbon atoms. An aryl group, an alkylaryl group and an aralkyl group; R? represents a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms; X represents an integer of 1 or 2; y represents an integer of 0, 丨 or 2; a, b And η represents an integer greater than or equal to 1, m and an integer greater than 〇], wherein each repeat is a block polymerization or a random polymerization; 〃 The method comprises the following steps: (a), four The acid monoanhydride is reacted with a diamine having a slow-acting group and/or a trans-functional group to obtain a poly-proline precursor having a carboxyl group and/or a hydroxyl group in the main chain; wherein the tetrabasic acid-anhydride is a diamine Moer Ratio for the tetracarboxylic dianhydride: two workers: 0.8~1: 1.2. (b) heating and cyclizing the polyproline precursor having a carboxyl group and/or a hydroxyl group in the main chain obtained in the above (a) to obtain a carboxyl group and/or a hydroxyl group having 1376395 polyimine in the main chain; And (ii) subjecting the hydroxyl group of the polyimine having a carboxyl group and/or a hydroxyl functional group in the main chain obtained in the above (b) to a dianhydride of the following formula to form an acid anhydride ring opening reaction: Λ Υ ο ( Π) (where R«= r9 'CR^^CRg-

r9 或 ^及RS可相同或不同且獨立為選自氫、鹵素、缓基、含㈣個 J之^鏈或環狀貌基、含6_2〇個碳原子之芳基、烧芳基及芳貌基，馬表不氫原子或含有！至6個碳原子之烷基），♦ 通式(1)麵重複單狀域上具有㈣酸基之聚酿亞知聚合物。〜^發明之方法巾’上述步驟⑻中所叙具有麟及/或經基吕^之=跡可使用僅具紐基官能基之二胺、僅 ίίϊΐ及同時具有絲及絲之官能基之二胺。於僅使用 ΟΗ有作物始二料’可麟上舰式附Α僅表示之U早位，且藉由控制二酸酐(π)之含量可控制瓜之值，例如-s_n)當量與雜當量相等時，m成為Q，於減當量大ί ’功成社於G。於觀啊具有減及祕 Ϊ ’可獲得上述通_中A表示0H及C_ )田里/、經基虽里相等時，m成為0，於羥基當量大於含二酸_)當量時’ m成為大於〇。 & 3 本發种具有残燒官能基之二胺為下列之二胺： 1376395 ch3 ch3 H2N—(0¾¾—Si—0—Si—(CH2)3 一 NH2, ch3 ch3 ch3 ch3 H2N—(CH2)4—Si—Ο-Si—(CH2)4—NH2, I I ch3 ch3 ch3 ch3 H2N—(CH2>j—Si—0—Si—(CHi)3—NH2, (1) (2) (3)R9 or ^ and RS may be the same or different and independently selected from the group consisting of hydrogen, halogen, slow-base, containing (four) J chain or cyclic base group, aryl group containing 6 2 〇 carbon atoms, aryl group and aromatic appearance Base, horse table is not hydrogen atom or contains! An alkyl group having up to 6 carbon atoms, ♦ a polymer of the formula (1) having a (iv) acid group on the monolithic domain. ~^Inventive method towel 'The above-mentioned step (8) has a lining and/or a kiln^================================================================================= amine. In the case of using only the first crop of the crop, the Kelin ship-type attachment only indicates the U early position, and the value of the melon can be controlled by controlling the content of the dianhydride (π), for example, -s_n) equivalent to the equivalent amount When m becomes Q, the reduction is equivalent to ί 'gong Chengshe in G. Yu Guan has the secret of reduction. 'The above-mentioned pass_A can be used to indicate 0H and C_.) When the base is equal, m becomes 0, and when the hydroxyl equivalent is greater than the diacid-containing equivalent, 'm becomes Greater than 〇. & 3 The diamine having a residual functional group is the following diamine: 1376395 ch3 ch3 H2N—(03⁄43⁄4—Si—0—Si—(CH2)3—NH2, ch3 ch3 ch3 ch3 H2N—(CH2) 4-Si-Ο-Si-(CH2)4-NH2, II ch3 ch3 ch3 ch3 H2N—(CH2>j—Si—0—Si—(CHi)3—NH2, (1) (2) (3)

CeHs CeHjCeHs CeHj

阳k厂IP (6) and f13 f13 r=\ 0CHr?iO-Si-ai2o—/ \ . U L, \_/~fYang k factory IP (6) and f13 f13 r=\ 0CHr?iO-Si-ai2o—/ \ . U L, \_/~f

本發明之,方法巾，上述步驟(咐糊之二胺， ⑺ 除了上述之具有缓基及/餘基额基之二胺及具 = 至進月$2:=步^之縮^反應係在常壓下於室溫 6_t；，較好在之環化反應係在能基之:胺可部份中有羧基及’或羥基官下，豆兩者間之t卜你丨卄么1軋烷s此基之二胺所置換之情況固内即可，但較好該具有矽氧烷官能基胺以又可胺之5〜60莫耳％，更好為10〜40莫耳％，最好為娜之聚酸亞胺聚合物可使用作為光阻劑，且於作為光阻二塗，於絲上例如織板上並_，彡縣後，认轉光後供因烘烤導致膜厚縮減。且本發明之聚醯亞胺聚合物因為感，性g能基直接接在高分子主鏈上，而具有較高^Td(9 μ、Λ發明又有關一種可制生感統酸亞胺樹月旨組成物，其包括述，之重複單位之水溶性感絲輕胺聚合物；⑻ (了基)丙稀酸單體稀釋劑；以及⑹光起始劑。其中成分⑷ 刀（B)之重里比例為1〇〇 : 1〇〜200，較好為1〇〇 : 4〇〜1〇〇。成分(〇 ^光起始劑，以成分⑷為⑽重量％時，其所含比例為aw5 〇重夏％ ’較好為1.0〜5.0重量〇/〇。【實施方式】 -本發财用以製備聚酿亞胺之方法步驟⑻巾賴之四幾酸二肝實例可舉例如(但不限於)2,2，·雙(H縣苯基)六氣丙烧二酐(6FDA)、苯均四酸二酐(pmda)、4,4，_氧基二酞酸酐 (ODPA)、3,3’，4,4’-聯苯四羧酸二酐(61>1)八）、3,3，，4,4，_二苯甲酮四緩酸二酐(BTDA)、伸乙基四舰二酐、丁烧四紐二針、環戊烷四羧酸二酐、2,2’，3,3，-二苯甲酮四羧酸二酐、2,2，，3,3，_聯苯四羧酸二針、2,2-雙(3,4-二羧基苯基)丙烷二酐、以雙似-工羧基苯基)丙烷二酐、雙(3,4-二羧基苯基)醚二酐、雙(3,4_二羧基苯基）颯二酐、1,1-雙(2,3-二羧基苯基)乙烷二酐、雙(2,3_二羧基苯基）曱烧二酐、雙(3,4_二羧基苯基)甲院二酐、4,4，_(對苯二氧基)二酞酸二針、,4,4’·(間-苯二氧基)二酞酸二酐、2,3,6,7—蔡四羧酸二肝、 1，4,5,8-萘四幾酸了野、l，2,5,6-萘四鲮酸二酐、ι,2,3,4-苯四羧酸二酐、3,4,9，10-二萘嵌苯四羧酸二酐、2,3,6,7-蒽四羧酸二酐及 1，2,7,8-菲四羧酸二酐等。該等二酸酐可單獨使用一種或以多種之混合物使用。其中較好為本發明中製備聚醯亞胺之方法步驟⑻中所使用之具有羧基及/或羥基官能基之二胺實例可舉例如(但不限於)例如3,5_二胺基 1376395 苯甲酸(DABZ)、3,3，_二絲_4,4’_二絲聯苯等。浐官亞胺之方法步驟⑻中所使用之具有石夕氧矽氧烧、Μ·雙(3-胺基苯氧基甲^U，3,3-四^基^氧烧t 雙(4-胺基苯氧基，基)-1山3,3-四〒基二石夕氧燒等£) ，美及/ΐΐΐΐΐϋ酿亞胺之方法步驟(a)中，除了上述之具有羧胺及具抑紐魏基之二胺以外之二 ϋ ί ί，ίϊ_苯基二胺㈣⑸、4,4，_氧基二苯胺(〇da)、 1，3-又(4-胺基本氧基)苯(TPE_R)、2，：雙本軋基）本(APB)、4,4’_雙(4-胺基苯氧基>33，_— ίί3其it f苯氧基)苯基]乙炫、2,2-雙[4-(3-胺基本氧基)本基]丙烷、2,2’-雙[4-(3-胺基苯氧基)苯基]丁烧、2 [4-(3-胺基苯氧基)苯基]_u山3,3,3_六氣丙院、4 4 苯^ 基)聯苯、雙[4_(3·胺基苯氧基)苯基]酮、雙 ^ 硫驗、雙[4_(3胺基苯蝴苯基胸、雙[4_(3_胺基3 苯氧基)苯細等。上述雙胺可單獨使^一‘ 本發明之製備雜亞胺之方法步驟⑻中，該二酸_ 反應可在非質子極性溶射進行，非f子極性溶劑之種類並無特 =制，只要不與反應物及產物反應即可。具體實例可如 2，Ν-二甲基乙醯胺(DMAc)、N_曱基吡咯烷酮_)、N，N_: 2’_F)、四氫呋喃(THF)、二噁烷、氯仿(CH二 N.吨細_及祕二甲基乙本發明之㈣輯亞胺之方法㈣(种，該二_與二胺之 11 1376395 反應一般在室溫至90°C，較好30至75°C之溫度範圍内進行。本發明之製備聚醯亞胺之方法中，於步驟(c)中，二酸肝可舉例為馬來酸酐、經取代之馬來酸酐、四氫鄰苯二甲酸酐、麪取代之四氫鄰苯二曱酸酐、甲撐鄰苯二曱酸酐、經：笨二曱酸酐等。州本發明之可丨谷性感光聚釀亞胺樹脂組成物中，成分田)之(甲丙烯酸單體稀釋劑除作為稀釋劑之功能以外，由於其分子内含有乙烯官能基，故亦有助於組成物照光後之硬化，其^例可例為例如乙二醇二丙烯酸酯、丙二醇二丙烯酸酯、丁二醇二丙酸酯、二乙二醇二丙烯酸酯、二丙二醇二丙烯酸酯、三羥^美丙烧三丙烯酸醋、三經乙基丙烧三丙稀酸醋、季戊二醋、二季戊四醇三丙稀_旨、乙二醇二甲基丙烯 :基丙烯咖、丁二醇二曱基丙埽義、二乙二醇二甲基丙稀酸酉_曰:一丙二醇二甲基丙稀酸g旨、三舒基丙燒三甲基丙稀酸醋、二？乙基丙烧三曱基丙騎g旨、季戊二甲基丙_酯、二季戊四醇二甲基丙烯酸醋等。，發明之聚醯亞胺樹脂於調製為光阻劑時，可調配有光起始刎。本發明之調配光阻組成物中所用的光起 ==外光、電子束以及Χ射線等輻射以Ϊ =結構會發生裂解產生如游離基、陽離子或陰離子等活性位點 (Acmve Slte)，而使聚醯亞胺及丙烯酸酯單體進行聚合反應者。光起始劑實例可舉例如♦蝴如2,2，雙(2_氯苯基° &广乙氧基Μ基笨基Η，2’·二味啥、2,2，_雙(2_漠苯基)-4:4，:5:5，-肆（·乙氧基羰基苯基)_1，2，_二咪唑、2 2，_雙Q 4 -蠢| 基 m，4’，5,5，-四笨基 _u，_ 二味 α坐、2,2，_’ 雙 ^ 2,2’-雙(2,4,6·三漠苯基M，4’，5,5，-四苯基八始 =例可舉例如三苯基膦氧化物_，可講自讎 △习），如雙(2,4,6-三甲基苯甲醯基)苯基膦氧化物㈣隱81, 12 1376395 (IR819) ’購自Ciba Geigy公司）；烷基苯基酮類，例如^羥基環己基苯基酮[如以Irgacure 184 (IR184)購自Ciba Geigy公司]、2-曱基-(4-曱基嗟吩基)-2-嗎琳-1-丙酿j[如以907 (JR907) 購自Ciba Geigy公司]等。光起始劑實例又可舉例如苯偶因(B enzo in)類光起始劑例如笨偶因、苯偶因甲基醚、苯偶因乙基醚、苯偶因異丙基醚、笨偶因異丁基醚、甲基-2-苯甲醯基苯曱酸酯等以及其類似衍生物。In the method of the present invention, the above steps (the diamine of the paste, (7) in addition to the above-mentioned diamine having a slow base and/or a base group, and having a reduction of the reaction amount of Pressurized at room temperature 6_t;, preferably in the cyclization reaction in the energy base: the amine can have a carboxyl group and 'or a hydroxyl group, the difference between the two of the beans. The substitution of the diamine of the base may be carried out, but it is preferred that the amine having a nonoxylamine functional group is 5 to 60 mol%, more preferably 10 to 40 mol%, more preferably Na's polyimidate polymer can be used as a photoresist, and it can be used as a photoresist for two coatings on silk, for example, on a woven board, and after 彡, after recognizing the light, the film thickness is reduced due to baking. Moreover, the polyimine polymer of the present invention has a higher ^Td (9 μ, Λ invention and a related sensitizing acid imide tree) because of the sensibility, the g-energy group is directly attached to the polymer main chain. a composition comprising a repeating unit of a water-soluble light-light amine polymer; (8) a (meth)acrylic acid monomer diluent; and (6) a photoinitiator. wherein the component (4) is a knife (B) ratio For example, 1〇〇: 1〇~200, preferably 1〇〇: 4〇~1〇〇. Ingredients (〇^光 initiator, when the component (4) is (10)% by weight, the ratio is aw5 〇 Heavy summer % ' is preferably 1.0 to 5.0 weight 〇 / 〇. [Embodiment] - The method for preparing the brewed imine in the present invention (8) The fourth embodiment of the liver is exemplified by (but not limited to) 2,2,·Shuang (H-phenyl) hexa-propylene dianhydride (6FDA), pyromellitic dianhydride (pmda), 4,4,-oxydiphthalic anhydride (ODPA), 3,3 ',4,4'-biphenyltetracarboxylic dianhydride (61>1) VIII), 3,3,,4,4,_benzophenone tetrazoic acid dianhydride (BTDA), extension ethyl four ship Di-anhydride, butyl sulphate, cyclopentane tetracarboxylic dianhydride, 2,2',3,3,-benzophenone tetracarboxylic dianhydride, 2,2,,3,3,_ Two needles of benzenetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, bis-carboxylphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl) Ether dianhydride, bis(3,4-dicarboxyphenyl)ruthenium anhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl) Terpinear dianhydride, bis(3,4-dicarboxyphenyl)methanhydride, 4,4, _( Two needles of p-phenylenedioxy)dicarbonate, 4,4'·(m-phenyldioxy)diphthalic acid dianhydride, 2,3,6,7-caitetracarboxylic acid dihepatic, 1,4 ,5,8-naphthalene tetraacid, wild, l, 2,5,6-naphthalene tetraphthalic acid dianhydride, iota, 2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10- Perylene tetracarboxylic dianhydride, 2,3,6,7-nonanetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, etc. These dianhydrides may be used alone or It is preferably used in a mixture of plural kinds. Among them, examples of the diamine having a carboxyl group and/or a hydroxyl functional group used in the step (8) of the method for producing a polyimine in the present invention are, for example, but not limited to, for example, 3,5. _Diamine 1376395 Benzoic acid (DABZ), 3,3, _difilament _4,4'-di-biphenyl. The method used in the step (8) of the sulphate imine has the sulphur-oxygen oxime, bismuth (3-aminophenoxymethyl), 3,3-tetrazyloxylated t-double (4- Aminophenoxy, yl)-1, 3,3-tetradecyl oxalate, etc., in the method step (a) of the US and/or brewing imine, in addition to the above-mentioned carboxyamine and ϋ ί ί ί ί ϊ 苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基苯基(TPE_R), 2,: double-rolled base) Ben (APB), 4,4'-bis (4-aminophenoxy) 33, _- ίί3, its it f phenoxy) phenyl] , 2,2-bis[4-(3-amine basic oxy)benyl]propane, 2,2'-bis[4-(3-aminophenoxy)phenyl]butane, 2 [4- (3-aminophenoxy)phenyl]_u mountain 3,3,3_hexapropene, 4 4 phenyl)biphenyl, bis[4_(3·aminophenoxy)phenyl]one , double sulphur test, bis [4_(3 aminophenylphenylphenyl), bis[4_(3-amino-3-phenoxy)benzene fine, etc. The above bisamine can be used alone to make the preparation of the present invention. In the imine method step (8), the diacid reaction can be carried out in an aprotic polar spray, and the non-f subpolar solvent The class is not specific, as long as it does not react with the reactants and products. Specific examples may be 2, Ν-dimethylacetamide (DMAc), N_mercaptopyrrolidone _), N, N_: 2' _F), tetrahydrofuran (THF), dioxane, chloroform (CH 2 N. ton fine _ and secret dimethyl ethene according to the invention (4) method of imine (4) (species, the bis and diamine 11 1376395 reaction Generally, it is carried out at a temperature ranging from room temperature to 90 ° C, preferably from 30 to 75 ° C. In the method for preparing a polyimine of the present invention, in the step (c), the diacid liver can be exemplified by maleic anhydride. Substituted maleic anhydride, tetrahydrophthalic anhydride, surface-substituted tetrahydrophthalic anhydride, methyl phthalic anhydride, by: stearic anhydride, etc. In the composition of the photosensitive light-polyimine resin, the component of the methacrylic acid monomer diluent (in addition to its function as a diluent, since the molecule contains an ethylene functional group, it also contributes to hardening of the composition after illumination). Examples thereof include, for example, ethylene glycol diacrylate, propylene glycol diacrylate, butanediol dipropionate, diethylene glycol diacrylate. Dipropylene glycol diacrylate, trihydroxy methacrylate, triacetic acid vinegar, triethyl ethion triacetate, pentaerythritol, dipentaerythritol tripropylene, ethylene glycol dimethyl propylene: Propylene coffee, butanediol dimercaptopropion, diethylene glycol dimethyl acrylate 酉曰一: propylene glycol dimethyl propylene acid g, trisyl propyl trimethyl acrylate vinegar乙乙乙乙烧三曱基丙骑 g, penta dimethyl propyl acrylate, dipentaerythritol dimethacrylate vinegar, etc., the invention of the polyimide resin can be prepared as a photoresist There is a light start 调. The light used in the formulated photoresist composition of the present invention == external light, electron beam, and xenon radiation, etc., and the structure is cleaved to generate an active site such as a radical, a cation or an anion, and A polymerization reaction is carried out by polymerizing a polyimide and an acrylate monomer. Examples of the photoinitiator can be, for example, a butterfly such as 2,2, bis(2-chlorophenyl ° & ethoxylated decyl hydrazino, 2'·dimiso, 2,2, _bis (2) _ desert phenyl)-4:4,:5:5,-肆(·ethoxycarbonylphenyl)_1,2,_diimidazole, 2 2,_double Q 4 -stupid | base m,4', 5,5,-四笨基_u,_ 二味α坐,2,2,_' double^ 2,2'-double (2,4,6·三漠phenyl M,4',5,5 , -tetraphenyl octagonal = for example, triphenylphosphine oxide _, can be said from 雠 △ ), such as bis (2,4,6-trimethylbenzylidene phenyl) phenyl phosphine oxide (4) Hid 81, 12 1376395 (IR819) 'purchased from Ciba Geigy Co., Ltd.; alkyl phenyl ketones, such as hydroxycyclohexyl phenyl ketone [as purchased from Ciba Geigy Inc. in Irgacure 184 (IR184)], 2-曱The base-(4-mercaptophenyl)-2-n-lin-1-propene-j is obtained from Ciba Geigy Co., Ltd. as 907 (JR907). Further examples of the photoinitiator include, for example, a benzoin-based photoinitiator such as a stupid couple, a benzoin methyl ether, a benzoin ethyl ether, a benzoin isopropyl ether, and a stupid Occasionally isobutyl ether, methyl-2-benzylidene benzoate, and the like, and similar derivatives thereof.

光起始劑實例又可舉例如苯乙酮類結構例如2,2-二甲氧基 -2-苯基苯乙酮[如以lrgacure 651 (IR651)購自Ciba Geigy公司]、 2-經基-2-曱基-1-苯基丙-1，、μ(4·異丙基苯基)_2_羥基_2_甲基丙 -1-酮、4_〇羥基乙氧基)笨基_(2_羥基_2_丙基)酮、2,2_二甲氧基苯乙_、2,2-二乙氧基苯乙_、2_节基_2_二曱胺基_ι·(4_嗎啉基苯基) y-l_酮、2,2’-二曱氧基·ΐ，2·二苯基乙+嗣、4_疊氮基苯乙酮、4· g氮基亞 >基笨乙目同等以及類似衍生物。光起始劑實例又可舉例如二苯曱酮類如二苯曱酮、4,4, _雙(二曱胺基)一苯甲酮、4,4’-雙(二乙胺基)二苯曱酮、3,3，·二甲基_4_ 甲氧基二苯甲酮等及其類似衍生物。光起始劑實例又可舉例如具有①二酮結構之光起始劑，例如Further examples of the photoinitiator include, for example, an acetophenone-based structure such as 2,2-dimethoxy-2-phenylacetophenone [e.g., from Ciba Geigy Co., Ltd. using lrgacure 651 (IR651)] -2-mercapto-1-phenylpropane-1, μ(4.isopropylphenyl)_2-hydroxy-2-methylpropan-1-one, 4-hydrazine hydroxyethoxy) stupyl _ (2-hydroxy-2-propenyl) ketone, 2,2-dimethoxyphenylethylidene, 2,2-diethoxyphenylethylidene, 2-phenylidene-2-diaminoamine- (4_morpholinylphenyl) y-l-ketone, 2,2'-dimethoxyoxyindole, 2,diphenylethyl fluorene, 4-azidoacetophenone, 4 g nitrogen Sub > Basic and similar derivatives. Further examples of the photoinitiator include, for example, benzophenones such as benzophenone, 4,4, bis(diamido)benzophenone, 4,4'-bis(diethylamino)di Phenyl ketone, 3,3, dimethyl 4-methyl benzophenone, and the like. Further examples of the photoinitiator include, for example, a photoinitiator having a diketone structure, for example

二乙醯基甲酸§旨、二苯帽基情酯、曱基苯曱醯基曱酸醋等以及類似衍生物； +具有多核醌結構之光起始劑如蒽醌、2_乙基蒽醌、2_第三了 U昆1,4秦酿等及類似衍生物；七頓類&姐也⑽e)結構之光起始劑如㈣酮、嗟_、2,4_二乙基侧酮、2_氯拥明等及類似衍生物；具有重氮結構之光起始劑如4_重氮二苯基胺、4_重氮_4，_ ίϋΪΪ、4_魏基士甲氧基二苯基胺等以及類似衍生物；有，n之光起始劑如2_(2，_吱喃基亞乙基)_4,6_雙(三氣甲 ί ψ氧絲乙烯基>4,6·雙(三解基)-s-三嗪如㈣基>s三.、2_(2,备4，_甲基苯基)-，x(_氯甲基>s•三嗓、…。塞吩基亞乙基)4,6_雙(三氣甲 13 1376395 基)-s-三嗪等以及類似衍生物。該等光起始劑可單獨使用亦可混合兩種以上使用。相對於成分(A)為1〇〇重量％計時，該光起始劑(C)之使用量為〇丨〜15 〇重量％，較好為1.0〜5.0重量％。本發明將以下列合成例以及實施例更進一步詳細說明，惟該Diethyl phthalic acid §, diphenyl cap base ester, mercaptobenzoyl phthalic acid vinegar, and the like; and a photoinitiator having a polynuclear fluorene structure such as hydrazine, 2_ethyl hydrazine 2_ third U Kun 1,4 Qin brewing and similar derivatives; seven classes & sister also (10) e) structure of light initiator such as (four) ketone, 嗟 _, 2, 4 _ diethyl ketone 2_Chlorobenzamine and the like; a photoinitiator having a diazo structure such as 4_diazodiphenylamine, 4_diazo _4, _ ί ϋΪΪ, 4 _ Wei Ke Shi methoxy Phenylamine and the like and similar derivatives; and, photoinitiator of n such as 2_(2,_吱-mercaptoethylidene)_4,6_bis (trisole gas)>4,6 · bis (trisyl)-s-triazine such as (tetra)yl >s three., 2_(2, prepared 4, _methylphenyl)-, x (_chloromethyl) s • triterpene,... .synylene, ethyl 4,6-bis (trisole 13 1376395)-s-triazine, and the like. These photoinitiators may be used alone or in combination of two or more. When the component (A) is 1% by weight, the photoinitiator (C) is used in an amount of 〇丨 15 15 % by weight, preferably 1.0 to 5.0% by weight. The following Synthesis Example will be further detailed description and examples, but the

等合成例以及實施例目的僅用以說明本發明而非用以限制本發明之範圍。 X 合成例1 將41.05克(0.1莫耳)之2,2，_雙-[4-(4-胺基苯氧基)苯基]丙烷 (BAPP)及9.14克(0.06莫耳)之3,5-二胺基苯曱酸(DABZ)及350 克N-甲基吼咯咬酮(N]y[p)置入1升玻璃反應瓶中，在室溫下激烈授^。加入88.48克(0.2莫耳)之2,2，·雙(3,4-二羧基苯基)六氟丙烧二酸軒(6FDA)於反應瓶中攪拌1小時後，再加入8.43克(0.039 f耳)3,3’-二羥基-4,4，-二胺基聯苯(HAP)，於室溫攪拌3小時。接著^加入50克甲苯，溫度增高至150°C反應24小時進行醯亞胺化 (環化)反應’獲得帶有OH基之聚醯亞胺，接著加入3.92克(〇.〇4 之馬來醯亞胺(MA) ’於室溫下繼續反應3小時。然後將該樹脂倒入大量甲醇中析出，可獲得136.2克聚醯亞胺聚合物 (pI_l)(產率:90.01%，IV 為 0.81，Td(95%): 340。〇。合成例2 15.215克(〇·ΐ莫耳)的3,5-二胺基苯甲酸(DABZ)和200克的The present invention is intended to be illustrative only and not to limit the scope of the invention. X Synthesis Example 1 41.05 g (0.1 mol) of 2,2,_bis-[4-(4-aminophenoxy)phenyl]propane (BAPP) and 9.14 g (0.06 mol) of 3, 5-Diaminobenzoic acid (DABZ) and 350 g of N-methylindole (N)y[p) were placed in a 1 liter glass reaction flask and vigorously incubated at room temperature. Add 88.48 g (0.2 mol) of 2,2,·bis(3,4-dicarboxyphenyl)hexafluoropropanone (6FDA) in the reaction flask for 1 hour, then add 8.43 g (0.039). f, 3,3'-dihydroxy-4,4,-diaminobiphenyl (HAP), stirred at room temperature for 3 hours. Then, 50 g of toluene was added, and the temperature was increased to 150 ° C for 24 hours to carry out a hydrazine imidization (cyclization) reaction to obtain a polyimine with an OH group, followed by the addition of 3.92 g (Malaysia of 〇.〇4) The reaction was continued for 3 hours at room temperature. Then the resin was poured into a large amount of methanol to obtain 136.2 g of a polyimine polymer (pI-1) (yield: 90.01%, IV was 0.81). , Td (95%): 340. 合成. Synthesis Example 2 15.215 g (〇·ΐ莫耳) of 3,5-diaminobenzoic acid (DABZ) and 200 g

ΝΜΡ置入il的玻璃反應斧中’在室溫下劇烈攪拌。加入4442 克(0.1莫耳)的2,2’-雙(3,4_二羧基苯基)·六氟丙烷二酸酐(6FDA) 和32.22克(〇.1莫耳)的3,3,4,4-二苯甲酮四羧酸二酐(BTDA)，於反應^擾拌1小時後，再加入21.19克(0.098莫耳)的3,3，-二羥基胺基聯^於室溫中攪拌3小時。然後加入3〇克的曱苯，提同溫度至15〇〇c反應24小時進行醯亞胺化(環化)反應，可得到一個帶有OH基的聚醯亞胺，然後再加入5 88克(〇〇6莫耳)的馬來^酐於室溫中繼續反應3小時。然後將該樹脂倒入大量甲醇中析，即可得到112.7g的聚醯亞胺聚合物$^2)(產率:94.8¾，IV 14 1376395 / 為 0.76，Td:336°C)。合成例3 15.215克(G.1莫耳)的3,5·二胺基苯ψ酸和3皿克(G G2莫之1，3-雙(3-胺基丙基;)-1，1，3,3-四曱基二矽氧烷(〇；51)及46〇克 NMP子入1L的玻璃反應斧中，在室溫下劇烈攪拌。加入32 22 克(0· 1莫耳)的3,3,4,4-二苯甲酮四羧酸二酐出万^和3 j 〇2克(〇工莫耳)的3,3,4,4-二苯基醚四羧酸二酐(〇DPA)於反應中攪拌丨小時後’再加入29.3克(0.08莫耳)的2,2·雙（3_胺基_4_經基苯基)六氟丙烧(BAFA)於室溫中擾拌3小時。然後加入克的甲苯，提高溫度至150°C反應24小時進行醯亞胺化(環化)反應，可得到帶有 • 0H基的聚趣亞胺，然後再加入5.88克(0.06莫耳)的馬來酸酐於室溫中繼續反應3小時。然後將該樹脂倒入大量曱醇中析出即可得到111.3g的聚醯亞胺聚合物^^3)(產率:92 3%，Iv為〇 67， Td:335〇C)。比較合成例1 * 41·05克(0.1莫耳)的2,2，-雙-(4-[4-胺基苯氧基]苯基)丙烷 (BAPP)和9.14克(〇.〇6莫耳)的3,5_二胺基苯甲酸⑼^)和35〇克的NMP置入1L的玻璃反應斧中，在室溫下劇烈攪拌。加入 88.84克(0_2莫耳）的2,2，_雙(3,4_二羧基苯基)六氟丙烷二酸酐籲（6FDA)於反應中攪拌1小時後，再加入8 43克(0.039莫耳)的3,3，- 二羥基-4,4’-二胺基·聯苯(hap)於室溫中攪拌3小時。然後加入 50克胃的f苯’提高溫度至丨就反應24小時，織將鑛脂倒入大畺甲醇中析出，即可得到137.3克的聚醯亞胺聚合物(pj_c) (產率:93.1% ’ IV 為 0.79，Td: 343。〇。Place the crucible into the glass reaction axe of il' vigorously stirring at room temperature. Add 4442 g (0.1 mol) of 2,2'-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and 32.22 g (〇.1 mol) of 3,3,4 , 4-benzophenone tetracarboxylic dianhydride (BTDA), after reacting for 1 hour, add 21.19 g (0.098 mol) of 3,3,-dihydroxylamine group at room temperature Stir for 3 hours. Then, 3 gram of terpene is added, and the reaction is carried out at a temperature of 15 〇〇c for 24 hours to carry out a hydrazine imidization (cyclization) reaction, thereby obtaining a polyimine with an OH group, and then adding 5 88 g. The maleic anhydride of (〇〇6 mol) was further reacted at room temperature for 3 hours. Then, the resin was poured into a large amount of methanol to obtain 112.7 g of a polyimine polymer (2) (yield: 94.83⁄4, IV 14 1376395 / 0.76, Td: 336 ° C). Synthesis Example 3 15.215 g (G.1 mol) of 3,5·diaminobenzoic acid and 3 g of g (G G2 1,3-bis(3-aminopropyl;)-1,1 , 3,3-tetradecyldioxane (〇; 51) and 46 g of NMP were placed in a 1 L glass reaction axe and stirred vigorously at room temperature. 32 22 g (0.1 mol) was added. 3,3,4,4-benzophenone tetracarboxylic acid dianhydride 3,3,4,4-diphenyl ether tetracarboxylic dianhydride of 10,000 and 3 j 〇 2 g (formerly molar) (〇DPA) After stirring for a few hours in the reaction, 'Additional 29.3 g (0.08 mol) of 2,2·bis(3-amino-4-yl-phenylphenyl)hexafluoropropane (BAFA) was added at room temperature. The mixture was stirred for 3 hours. Then, gram of toluene was added, and the temperature was raised to 150 ° C for 24 hours to carry out the oxime imidization (cyclization) reaction, and the poly-imine with ? 0 group was obtained, and then 5.88 g was added. The maleic anhydride (0.06 mol) was further reacted at room temperature for 3 hours, and then the resin was poured into a large amount of methanol to precipitate 111.3 g of a polyimine polymer (3) (yield: 92). 3%, Iv is 〇67, Td: 335〇C). Comparative Synthesis Example 1 * 41.05 g (0.1 mol) of 2,2,-bis-(4-[4-aminophenoxy]phenyl)propane (BAPP) and 9.14 g (〇.〇6 Mo The ear 3,5-diaminobenzoic acid (9)^) and 35 g of NMP were placed in a 1 L glass reaction axe and stirred vigorously at room temperature. Add 88.84 g (0-2 mol) of 2,2,_bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and stir for 1 hour in the reaction, then add 8 43 g (0.039 mo) The 3,3,-dihydroxy-4,4'-diaminobiphenyl (hap) of the ear was stirred at room temperature for 3 hours. Then, 50 g of f benzene of the stomach was added to increase the temperature until the reaction was carried out for 24 hours, and the petrolatum was poured into a large methanol to precipitate, and 137.3 g of a polyimine polymer (pj_c) was obtained (yield: 93.1). % 'IV is 0.79, Td: 343. 〇.

上述合成例及比較例之反應物、其量及其物理數據概述於下合成例1 (H-1) 合成例2 (PI-2) 合成例3 (PI-3) 比較合成例 1(PI-C) BAPP(莫耳） 0.1 0.1 15 1376395 DABZ(莫耳） 0.06 0.1 0.1 0.06 HAP (莫耳） 0.039 0.098 0.039 BAFA(莫耳） 0.08 6FDA(莫耳） 0.2 0.1 0.2 BTDA(莫耳） 0.1 0.1 ODPA(莫耳） 0.1 MA(莫耳） 0.04 0.098 0.06 DSI 0.02 IV(特性黏度） 0.81 0.76 0.67 0.79 Td(95%)(°C) 340 336 335 343 製造例1感光光阻保護膜(Coverlay)之製作 2〇克的PI-卜0·8克的IR651(光聚合起始劑）、7.2克的乙二醇二丙烯酸酯(M-1)和2.8克的三羥乙基丙烷三甲基丙烯酸酯 (M-2)，溶解於I24g的NMP，並於室溫攪拌3小時後，即可得到感光Η膠(V-1)。使用刮板塗佈(間隙=1〇〇μιη)將ΡΙ膠塗佈在聚苯二甲酸乙二酯(PET)上:並以90。(：/13分鐘烘烤。將其烘烤後的ΡΙ膜在轉印機上以120°C、壓力1 kgfcm與銅箔壓合。將此積層物具有所需The reactants, amounts and physical data of the above synthesis examples and comparative examples are summarized in the following Synthesis Example 1 (H-1) Synthesis Example 2 (PI-2) Synthesis Example 3 (PI-3) Comparative Synthesis Example 1 (PI- C) BAPP (Mole) 0.1 0.1 15 1376395 DABZ (Mohr) 0.06 0.1 0.1 0.06 HAP (Mohr) 0.039 0.098 0.039 BAFA (Moule) 0.08 6FDA (Mohr) 0.2 0.1 0.2 BTDA (Mole) 0.1 0.1 ODPA (mole) 0.1 MA (mole) 0.04 0.098 0.06 DSI 0.02 IV (intrinsic viscosity) 0.81 0.76 0.67 0.79 Td (95%) (°C) 340 336 335 343 Production Example 1 Photomask Protective Film (Coverlay) 2 g of PI-Bu 0. 8 g of IR651 (photopolymerization initiator), 7.2 g of ethylene glycol diacrylate (M-1) and 2.8 g of trishydroxyethylpropane trimethacrylate ( M-2), dissolved in I24g of NMP, and stirred at room temperature for 3 hours, then the photosensitive gelatin (V-1) was obtained. The silicone was coated on polyethylene terephthalate (PET) using a squeegee coating (gap = 1 〇〇 μηη): and at 90. (:/13 minutes baking. The baked film was pressed on a transfer machine at 120 ° C and a pressure of 1 kgfcm. The laminate was required.

圖案之透過光罩以紫外線曝光裝置(型號〇RC_〇B_1〇〇〇，〇RC MANUPACTRUINGCO.製造)進行曝光(500mJ/cm2)，並用 i 加％The pattern is exposed to a light-shielding device (model 〇RC_〇B_1〇〇〇, manufactured by 〇RC MANUPACTRUINGCO.) for exposure (500 mJ/cm2), and i is added with %

Na2C03水溶液進行顯影2分鐘，再浸泡於純水中洗 HKTC/1小時，150〇C/1小時，2〇(TC/1小時，挪⑵小時烘烤。藉由放大鏡及電子掃描顯微鏡觀察所得光阻圖案，密著為100/10〇Mm的線路圖。㈣Γ传到解析/ 溶解度試驗：，所得聚醢亞胺洗鎢成臈，取尺寸9*55咖2溶解於佳右超過2分鐘仍留有未溶解物，則表示為溶解度，，不 1376395 襲造例2感光光阻保護膜之製作口/ΛΥ=α75克的1^7(汽巴嘉基翻化學品公司两，，細嗣)、6克的乙二醇二丙軸旨二3 = ，羥乙基丙烷三甲基丙烯酸酯’ 2 5g的季戊四二丙酉^3)溶解於13〇g的nmp，並於室溫擾掉3 *時後= ΓΓ:2)。賴狀齡職观轉麟解度‘ 製造例3感光光阻保護膜之製作The Na2C03 aqueous solution was developed for 2 minutes, and then immersed in pure water for HKTC/1 hour, 150 〇C/1 hour, 2 〇 (TC/1 hour, for 2 hours). The light was observed by a magnifying glass and an electron scanning microscope. Resistance pattern, densely lined with 100/10〇Mm. (4) Γ 到 to analysis / Solubility test: The obtained polythene imide is washed into tungsten, taking the size of 9*55 coffee 2 dissolved in Jiayou for more than 2 minutes still left In the case of undissolved matter, it is expressed as solubility. It is not 1376395. In the case of the production of the photoreceptor protective film of the example 2, the 口=ΛΥ=α75g of the 1^7 (Cibajiaji Chemicals Co., Ltd., two), 6 Gb ethylene glycol dipropyl axis 2 3 =, hydroxyethyl propane trimethacrylate '25 g of pentaerythritol ^ 3) dissolved in 13 〇 g of nmp, and disturbed at room temperature 3 * After the time = ΓΓ: 2). Lai's age, attitude, and tempering degree

20 克的 PI-3、0.53 克的 IR907、0.2 克的 ΙΤΧ、3·5 克的乙二醇二丙，酸酯(Μ-1)和3.4克的季戊四醇二丙婦酸醋_)和^ 克的異氰尿酸二(乙烧丙嫦酸g旨)(Μ-4)溶解於119克的jsj]y[p，並於室溫攪拌3小時後，即可得到感光性PI膠(¥3)。保護膜之製作及NafO3水溶液溶解度試驗與製造例1相同。、比較製造例1感光光阻保護膜之製作 20克的PI-C、0.8克的111651(2,2-二甲氧基_2_苯基苯乙酮）、 7.2克的乙二醇二丙烯酸酯(M4)和28克的三羥乙基丙烷三甲基丙烯酸酯(M-2) ’溶解於124克的NMP，並於室溫攪拌3小時後，即可得到感光PI膠(V-C)。保護膜之製作及Na2C03水溶液溶解度試驗與製造例1相同。感光光阻保護膜之調配比例以及溶解度試驗結果示於下表 2 ° 表2 成分(克）製造例1 (V-1) 製造例2 (V-2) 製造例3 (V-3) 比較製造例 1(V-C) 樹脂 PI-1 (100) PI-2 (100) PI-3 (100) PI-C (100) IR651 4.0 4.0 IR907 - 3.75 2.65 ΓΓΧ_ 0.75 1.0 Μ-1 — 36.0 30.0 17.5 36.0 17 1376395 M-2 M-3 M-4 解析度膜厚縮減率(%) Na2C03水溶液中之溶解度 14.0 17.5 12.5 14.0 100/100μιη 約11% 佳 80/100μιη 約7% 佳 17.0_ 10.5_ 100/100μιη 約 8°/〇佳 200/250μπι 約10% 不佳表可知，本發批感級 ^帶有感絲宫能基’且具有酸基故對於 ^ 外，T感紐官能基直接連接在聚合物主鏈顯影後，也不會_烤導致膜厚嚴重縮減：、【主要元件符號說明】20 grams of PI-3, 0.53 grams of IR907, 0.2 grams of bismuth, 3.5 grams of ethylene glycol dipropylene, ester (Μ-1) and 3.4 grams of pentaerythritol dipropylene vinegar _) and gram Isocyanuric acid di(ethyryl citrate) (Μ-4) was dissolved in 119 g of jsj]y[p, and stirred at room temperature for 3 hours to obtain a photosensitive PI gel (¥3). . The production of the protective film and the solubility test of the aqueous solution of NafO3 were the same as in Production Example 1. Comparative Production Example 1 Photoresist Protective Film Manufactured 20 g of PI-C, 0.8 g of 111651 (2,2-dimethoxy-2-phenylacetophenone), and 7.2 g of ethylene glycol diacrylate The ester (M4) and 28 g of trishydroxyethylpropane trimethacrylate (M-2) were dissolved in 124 g of NMP and stirred at room temperature for 3 hours to obtain a photosensitive PI gel (VC). The production of the protective film and the solubility test of the aqueous solution of Na2C03 were the same as in Production Example 1. The ratio of the photosensitive resist protective film and the solubility test results are shown in the following table 2 ° Table 2 Composition (g) Manufacturing Example 1 (V-1) Manufacturing Example 2 (V-2) Manufacturing Example 3 (V-3) Comparative Manufacturing Example 1 (VC) Resin PI-1 (100) PI-2 (100) PI-3 (100) PI-C (100) IR651 4.0 4.0 IR907 - 3.75 2.65 ΓΓΧ_ 0.75 1.0 Μ-1 — 36.0 30.0 17.5 36.0 17 1376395 M-2 M-3 M-4 Resolution Film Thickness Reduction Rate (%) Solubility in Na2C03 Aqueous Solution 14.0 17.5 12.5 14.0 100/100μιη Approx. 11% Good 80/100μιη Approx. 7% Good 17.0_ 10.5_ 100/100μιη Approx 8 ° / 〇 good 200 / 250μπι about 10% poor table shows that the first batch of sensory level ^ with the sensation of the ruthenium and has an acid group, so the T-sensitive functional group is directly connected to the polymer backbone After development, it will not be _baked and the film thickness will be seriously reduced: [Main component symbol description]

Claims

第097151347號專利申請案申請專利範圍替換本(101年8月）公竟§ Μ年》月d日修正本亞胺聚合物’其特徵為具有下之重複-Patent Application No. 097151347 Patent Application Substitute Replacement (August 101) Public § Μ 》》月日修正修正亚亚亚亚亚亚亚亚亚亚亚亚亚亚亚亚亚亚亚亚

七、申請專利範圍： 1· 一種水溶性感光聚醯單位： mRi為含有4個以上碳原子之四價有機基；r2為3價或媳i機基其上可視情況又帶有致基；R3表示1價至4價有表示0H或⑽㈣：心及^可相同亦可不同，分 # 為合1至6個碳原子之伸烷基、含6至20個碳原子之申方基、伸芳烧基、伸芳氧基伸烷基；RjR8可相同或不同 =獨立為選自氫、較、絲、含12()個礙之直鏈或環狀烧㈣個碳原子之芳基、絲基及芳絲；R9表示氫原 t或含有、1至6個碳原子之烧基；X表示1或2之整數；y表示〇 1或2之整數；a、b及η表示大於或等於1之整數；m 表示大於等之整數];且上述各重複單位可為嵌段聚 s亦可為隨機聚合。 1 ’ 请專利範圍第1項之水溶性感光聚醯亞胺聚合物，其中其平均分子量為1〇〇〇〇〜3⑻，〇〇〇，其特性黏度(IV)為 • :0.95且其5%熱重損失溫度(Td (95%))高於3〇(rc。 •如申=專利範圍第1項之水溶性感光聚醯亞胺聚合物，.其中當將水溶性感光性聚醯亞胺聚合物塗佈成膜厚為10〜25μιη之薄膜第097151347號專利申請案申請專利範圍替換本(101年8月） =’將膜片尺寸9*5.5cm2溶解於1000毫升之lwt%碳酸鈉水溶液中之溶解時間少於2分鐘。 4.種製備具有下式(I)之重複單位之水溶性感光聚醯亞胺聚合物之方法，VII. Patent application scope: 1. A water-soluble photosensitive polyfluorene unit: mRi is a tetravalent organic group containing 4 or more carbon atoms; r2 is a trivalent or 媳i machine base, and it may have a radical on the substrate; R3 represents The valence of 1 to 4 represents 0H or (10) (4): the heart and the ^ may be the same or different, and the fraction # is an alkyl group having 1 to 6 carbon atoms, a base group having 6 to 20 carbon atoms, a aryl group, Aryloxyalkylene; RjR8 may be the same or different = independently selected from hydrogen, relatively, silk, 12 () linear or cyclic (four) carbon atoms of aryl, silk and aromatic filaments; R9 represents hydrogenogen t or a group containing 1 to 6 carbon atoms; X represents an integer of 1 or 2; y represents an integer of 〇1 or 2; a, b and η represent an integer greater than or equal to 1; m represents An integer greater than or equal to each other; and each of the above repeating units may be a block poly s or may be a random polymerization. 1 ' Please refer to the water-soluble photosensitive polyimide polymer of the first item of the patent range, wherein the average molecular weight is 1〇〇〇〇~3(8), and the intrinsic viscosity (IV) is: 0.95 and 5% thereof. The thermogravimetric loss temperature (Td (95%)) is higher than 3 〇 (rc. • The water-soluble photosensitive polyimide polymer according to claim 1 of the patent range, wherein the water-soluble photosensitive polyimide The polymer is coated into a film having a film thickness of 10 to 25 μm. Patent Application No. 097151347 Patent Application No. (August, 2011) = 'Dissolve the film size 9*5.5 cm2 in 1000 ml of a lwt% sodium carbonate aqueous solution The dissolution time is less than 2 minutes. 4. A method for preparing a water-soluble photosensitive polyimine polymer having a repeating unit of the following formula (I),

CRp=CR8-、CRp=CR8-,

[式jt7 為含有4個以上碳原子之四價有機基；r2為3價或 4價有機基，其上可視情況又帶有羧基；馬表示2價至4價有機基；A表示OH或COOH基；仏及R5可相同亦可不同，分別表示為含1至6個碳原子之伸烧基、含6至2〇個碳原子之伸芳基、、伸芳烧基、伸芳氧基伸烧基；尺7及心可相同或不同且獨立為選自鼠、鹵素、幾基、含1-20個碳之直鏈或環狀烧基、含6-20個碳原子之芳基、烷芳基及芳烷基；^表示氫原子或含有1至6個碳原子之烧基；X表示1或2之整數；y表示〇、1或2之整數；a、b及η表示大於或等於i之整數；m 及k表示大於等於〇之整數];其中各重複單為可為嵌段聚合或無規聚合；該方法包括下列步驟： (a)使四羧酸二酐與具有羧基及/或羥基官能基之二胺在常壓下於至溫至90C進行反應’獲得主鍵上具有竣基及/或經基 B月b基之聚酿胺酸月驅物，其中四幾酸二野對二胺之莫耳舍量比為四羧酸二酐：二胺=1 : 0.8〜1 : 1.2 ; 、田第097151347號專利申請案申請專利範圍替換本(101年8月） (b) 使上述(a)所得之主鏈上具有羧基及/或羥基官能基之聚醯胺酸前驅物在60〜200°C之溫度進行加熱環化，獲得主鏈上具有羧基及/或羥基官能基之聚醯亞胺；及 (c) 使上述(b)所得之主鏈上具有縣及/或經基官能基酿亞胺中之㉟基與下式(11)之二麵進行贿之開環反應：[Formula jt7 is a tetravalent organic group containing 4 or more carbon atoms; r2 is a trivalent or tetravalent organic group, which may optionally have a carboxyl group; a horse represents a divalent to tetravalent organic group; and A represents an OH or COOH group;仏 and R5 may be the same or different, respectively represented as a stretching group having 1 to 6 carbon atoms, an extended aryl group having 6 to 2 carbon atoms, an exoaryl group, and an extended aryloxy group. The base 7 and the core may be the same or different and independently selected from the group consisting of a mouse, a halogen, a group, a linear or cyclic alkyl group having 1 to 20 carbons, an aryl group having 6 to 20 carbon atoms, and an alkyl group. And aralkyl; ^ represents a hydrogen atom or a burnt group having 1 to 6 carbon atoms; X represents an integer of 1 or 2; y represents an integer of 〇, 1 or 2; and a, b and η represent greater than or equal to i An integer; m and k represent an integer greater than or equal to ]]; wherein each repeat sheet may be a block polymerization or a random polymerization; the method includes the following steps: (a) subjecting the tetracarboxylic dianhydride to having a carboxyl group and/or The hydroxy-functional diamine is subjected to a reaction at a temperature of up to 90 C under normal pressure to obtain a melamine group having a sulfhydryl group and/or a B group of a base b group, wherein the tetrabasic acid is The molar ratio of the diamine to the diamine is tetracarboxylic dianhydride: diamine = 1: 0.8~1: 1.2; the patent application scope of the patent application No. 097151347 (August, 2011) (b) The polyproline precursor having a carboxyl group and/or a hydroxyl group in the main chain obtained in the above (a) is heated and cyclized at a temperature of 60 to 200 ° C to obtain a carboxyl group and/or a hydroxyl group in the main chain. Polyimine; and (c) subjecting the main chain of the above (b) to a ring-opening reaction of a 35-group of a county- and/or trans-functional aryl imino group to the two sides of the following formula (11) :

(II) r9(II) r9

RgRg

或鹵素、羧基、含1-20 (式中，R6= -CRp=CR8-- 、 R7及118可相同或不同且獨立為選自氫m吞、t m -石ίΐ直環狀燒基、含6-20個碳原子之芳基、烧芳基及 fii 9表核原子或含有1至6個碳原子之絲）；胺述通式(1)表示重複單位之具有丙烯酸基之聚醯亞 5· ^申，專利範圍第4項之方法’其中上述步驟⑻幅用之且有^及/或經基官能基之二胺係具有經基及絲之官能基^ -0 6 項之方法，其中上述步驟⑻中所用之具二胺所置^莖土目能基之二胺係部份經具有矽氧烷官能基之利範圍第6項之方法，其中該具有魏烧官能基之二胺佔所有二胺之5〜60莫耳〇/0。圍第I項之方法’其中該具树姐官能基之二 ms/、、!自&，3·雙(3_胺基丙基>u，3,3·四甲基二石夕氧烧胺美而其t雙胺基丁基^1’1，3,3’四甲基二石夕氧烧' I3-雙(3_ ^ 土 ·ι，3_一曱基_1，3-二苯基二石夕氧烧、1，3_雙(3_胺其笨土Μ，1，3,3·四曱基二石夕氧燒、u娜_胺基苯基甲申請專利範圍替換本(101年8月') 、1，3_雙(3_胺基苯氧基甲基)_u，3,3_四甲基二 ί：之組氧基甲基^讲四甲基二魏燒所組筋光聚亞胺樹脂組成物，其包括(Α)如中請專利合物；之水雜感缺酿亞胺聚 ..(Λ) ：以糊物Q_鱗，歸Or halogen, carboxyl group, containing 1-20 (wherein R6=-CRp=CR8--, R7 and 118 may be the same or different and independently selected from hydrogen m-ton, tm-stone, ortho-ring, including 6 An aryl group of -20 carbon atoms, an aryl group and a fii 9 core or a filament having 1 to 6 carbon atoms; an amine of the formula (1) represents a repeating unit of an acrylic group having an acrylic group. The method of the fourth aspect of the invention, wherein the above-mentioned step (8) and the diamine having a functional group have a functional group of a base and a silk, wherein the above The diamine moiety having a diamine in the step (8) is subjected to the method of the sixth aspect of the dioxane functional group, wherein the diamine having a Wei-burning functional group accounts for 5 to 60 moles of diamine / 0. The method of the first item, wherein the two of the functional groups of the tree sister are ms/, , ! from &, 3·bis (3_aminopropyl)>u, 3,3·tetramethyldish Ethanol and its t-diaminobutyl ^1'1,3,3' tetramethyl bismuth oxylate ' I3-double (3_ ^ 土·ι,3_一曱基_1,3-二Phenyl sulphate, 1,3 bis (3_amine, stupid sputum, 1,3,3·tetradecyl sulphate, u na-aminophenyl A (August 101 '), 1,3_bis(3_aminophenoxymethyl)_u, 3,3_tetramethyl 2: group of oxymethyl groups The composition of the ribonuclear polyimine resin, which comprises (Α) such as the patent compound; the water miscellaneous lack of the imine poly.. (Λ): with the paste Q_ scale, return