TW583161B - Base-proliferation prepolymers - Google Patents
Base-proliferation prepolymers Download PDFInfo
- Publication number
- TW583161B TW583161B TW90126301A TW90126301A TW583161B TW 583161 B TW583161 B TW 583161B TW 90126301 A TW90126301 A TW 90126301A TW 90126301 A TW90126301 A TW 90126301A TW 583161 B TW583161 B TW 583161B
- Authority
- TW
- Taiwan
- Prior art keywords
- alkali
- prepolymer
- proliferative
- composition
- ministry
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/20—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Resins (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
583161 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（1) 本發明係有關藉由鹼作用產生鹼之鹼增殖性預聚物、 驗增殖性預聚物組成物、鹼反應性組成物、感光性組成物 、高分子模式形成方法及高分子成型品之製造方法者。 先行技術中，有感於活性能量線之樹脂或其組成物係 以藉由光、紅外線、遠紅外線、電子線、或X線等活性線 之作用產生之化學性結構變化做爲畫像形成材料之用，或 以單體、預聚體之硬化用於表面被覆處理等，於多領域被 實用化。活性線中，被廣泛使用者爲光，以下特定以光說 明活性能量線，惟，針對本發明樹脂或其組成物之活性能 量線並非僅限於光者。 目前爲止，藉由單體、預聚體之活性能量線爲提昇硬 化速度而嘗試各種方法。最被廣泛開發之對象爲以光作用 產生之原子團種做爲啓始劑，連續性聚合多數乙嫌基單體 之光聚合系者。又，光作用所產生之酸，此酸做爲觸媒之 陽離子聚合系亦爲被極力開發之對象。惟，陽離子聚合系 時，藉由空氣中之氧阻斷聚合反應，特別於薄膜系中抑制 硬化，因此，務必特別進行氧之阻斷。另外，陽離子聚合 系中，未有此氧阻斷效果爲較佳者，惟，由酸產生劑所產 生之強酸於硬化後仍殘存之，因此，其腐蝕性、樹脂之變 性問題出現。 又，藉由光、電子線組合照射與熱處理之混種型硬化 技術亦同樣廣泛實用於表面被覆物之高速處理，無溶媒製 造流程者。更且，潛在性使酸、鹼裝置熱產生原理之液性 感熱硬化樹脂組成物亦被做爲討論對象，而，由省能量之 n· ml 1·—— K ϋϋ· in IK a·.—· 士i^i— ϋϋ i·—— ϋϋ 11· 1"J (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） _ 4 _ 583161 A7 經濟部智慧財產局員工消費合作社印製 ______B7_五、發明説明（2 ) 觀點視之，以熱處理過程之硬化最爲迅速者爲被期待者。 做爲克服此問題點方法之一者如：藉由鹼觸媒之聚合 反應、化學反應之使用被提出。如：藉由光、熱作用產生 鹼，以此做爲觸媒使樹脂進行化學變性之方法。如：具環 氧基之化合物藉由鹼作用引起交聯反應，因此，藉由光、 熱作用使做爲啓始劑、觸媒之胺類於環氧系樹脂層內產生 ，再藉由加熱處理等進行硬化之方法者。惟，藉由活性能 量線作用其硬化速度低，因此，尙未能實用化。 如此，利用活性能量線爲迅速使液狀物呈固化或硬化 之硬化技術可更高性能化者，因此被強烈要求不藉由空氣 中氧之阻斷效果，不含如所生成強酸之腐蝕性物質，更可 以高效率進行反應者。 觸媒反應中，關於其觸媒分子之數未變化，因此，藉 由不明中毒作用後，觸媒失活而停止反應。或固體中之擴 散被強行抑制，亦停止反應。因此，爲使觸媒反應更高效 率化時，只要於觸媒反應過程中增加具有觸媒作用之分子 數即可。亦即，自體觸媒分解後，出現具有新觸媒能之分 子產生物質即可。實際上，目前爲止，被提出有自體觸媒 分解後產生強酸，強酸濃度具有非線形性增大之特性之酸 增殖反應（特開平8 - 248456 1 ，有光晃二、市村 國宏、組裝增殖反應之高感度有機系光畫像形成材料、機 能材料、17(12) ，16 — 24(1997))。此 增殖性增加酸之酸增殖劑被發現，藉由添加此等後，意圖 取得高性能化之樹脂組成物者亦爲公知者（Koji Arimitu 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） _ 5 _ n I I 衣— I I 訂— I I I —.^ %?- (請先閱讀背面之注意事項再填寫本頁) 583161 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（3 ) Chimura, J. Am. Chem. Soc. 120, 37-45(1998)) 〇 因此，本發明者針對藉由鹼作用後自體分解產生新的 鹼之鹼增殖反應、及實現此之鹼增殖劑所有發現進行精密 硏討後，其結果發現，某種尿烷衍生物實際上可引起鹼增 殖反應（M· Miyamoto, K. Arimitu and K. Ichi mura, J. photopolym Sci· Technol·，12，3 1 5( 1999)及 K. Arimitsu，Μ· Miyamoto and K. Ichimura, J. photopolym Sci Technol., 12, 3 1 5( 1 999))。此增殖反應所產生之鹼主要爲1級或2級之脂 肪族胺者，較富揮發性者。爲有效進行此鹼增殖反應，一 般務必進行加熱處理。因此，增殖反應所產生之胺於此開 放系之加熱處理過程中出現蒸發飛散，如：進行環氧樹脂 之胺硬化時，無法出現充份添加鹼增殖劑效果之問題點。 本發明係以提供一種新穎的鹼增殖性預聚物、鹼增殖 性預聚物組成物、鹼反應性組成物，利用該鹼反應性組成 物之高分子模式形成方法及利用該鹼反應性組成物之高分 子成型品的製造方法爲課題者。 本發明者爲解決該課題，經精密硏討結果後完成本發 明。 亦即，本發明係提供一種藉由如下記式（1 )所示之 鹼作用後產生鹼之鹼增殖性預聚物。583161 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (1) The present invention relates to alkali-proliferative prepolymers that produce alkalis through the action of alkalis, proliferative pre-polymer compositions, and alkali reactivity. A composition, a photosensitive composition, a method for forming a polymer pattern, and a method for producing a polymer molded product. In the prior art, resins or their compositions that are sensitive to active energy rays use chemical structure changes caused by the action of active rays such as light, infrared, far infrared rays, electron rays, or X-rays as materials for image formation. It can be used in various fields such as hardening of monomers and prepolymers for surface coating treatment. Among the active rays, light is widely used by the users, and light is used to describe the active energy rays. However, the active energy rays for the resin or the composition of the present invention are not limited to light. So far, various methods have been tried to increase the hardening speed by using active energy rays of monomers and prepolymers. The most widely developed object is the photopolymerization system that uses the atomic species produced by light as the initiator to continuously polymerize most ethyl monomers. In addition, the acid produced by the action of light, and this cationic polymerization system as a catalyst is also an object to be vigorously developed. However, in the cationic polymerization system, the polymerization reaction is blocked by oxygen in the air, and the hardening is suppressed particularly in the thin film system. Therefore, it is necessary to specifically block the oxygen. In addition, in the cationic polymerization system, there is no one that has the better oxygen blocking effect. However, the strong acid generated by the acid generator still remains after hardening. Therefore, the problems of its corrosiveness and resin deformation appear. In addition, the mixed-type hardening technology by combining light and electron beam irradiation and heat treatment is also widely used in high-speed processing of surface coatings and solvent-free manufacturing processes. In addition, the liquid heat-curable resin composition that potentially causes the heat generation principle of acid and alkali devices is also discussed, and the energy-saving n · ml 1 · —— K ϋϋ · in IK a · .— · 士 i ^ i— ϋϋ i · —— ϋϋ 11 · 1 " J (Please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) _ 4 _ 583161 A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ______ B7_ V. Description of the invention (2) From the viewpoint, the person who has the most rapid hardening in the heat treatment process is the one who is expected. As one of the methods to overcome this problem, for example, the use of alkali-catalyzed polymerization and chemical reactions has been proposed. For example, alkali is generated by the action of light and heat, which is used as a catalyst to chemically modify the resin. For example, compounds with epoxy groups cause cross-linking reactions by the action of bases. Therefore, amines used as initiators and catalysts are generated in the epoxy resin layer by the action of light and heat, and then heated by Methods such as hardening. However, since the hardening speed is low due to the action of active energy rays, thorium cannot be put into practical use. In this way, the hardening technology that uses the active energy ray to rapidly solidify or harden the liquid object can be more highly performant, so it is strongly required that it does not rely on the blocking effect of oxygen in the air and does not contain the corrosiveness of the strong acid generated Material, it can react more efficiently. In the catalyst reaction, the number of catalyst molecules has not changed. Therefore, after unknown poisoning, the catalyst is deactivated to stop the reaction. Or the diffusion in the solid is forcibly suppressed and the reaction is also stopped. Therefore, in order to make the catalytic reaction more efficient, it is only necessary to increase the number of molecules having a catalytic effect during the catalytic reaction. That is, after the autocatalyst is decomposed, a molecular-producing substance having a new catalyst energy may appear. In fact, so far, it has been proposed that the acid proliferates after the decomposition of the autocatalyst to produce a strong acid, and the strong acid concentration has a characteristic of increasing non-linearly. High-sensitivity organic photoimage forming materials, functional materials, 17 (12), 16-24 (1997)). This acid-proliferative acid-promoting agent has been found, and by adding these, those who intend to obtain high-performance resin compositions are also known (Koji Arimitu This paper applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm) _ 5 _ n II clothing — II order — III —. ^%?-(Please read the notes on the back before filling out this page) 583161 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Description of the invention (3) Chimura, J. Am. Chem. Soc. 120, 37-45 (1998)) Therefore, the present inventors aimed at the base proliferation reaction and the realization of a new base by autolysis by the action of a base After all the findings of this base multiplier were carefully discussed, it was found that a certain urethane derivative can actually cause a base multiplication response (M. Miyamoto, K. Arimitu and K. Ichi mura, J. photopolym Sci. Technol ·, 12, 3 1 5 (1999) and K. Arimitsu, M. Miyamoto and K. Ichimura, J. photopolym Sci Technol., 12, 3 1 5 (1 999)). The base produced by this proliferation reaction is mainly a class 1 or 2 aliphatic amine, which is more volatile. In order to effectively carry out this alkaline proliferation reaction, heat treatment is generally necessary. Therefore, the amine produced by the proliferation reaction evaporates during the heat treatment of this open system. For example, when the amine hardening of the epoxy resin is performed, the problem of the effect of fully adding an alkali proliferation agent cannot occur. The invention aims to provide a novel alkali-proliferative prepolymer, alkali-proliferative pre-polymer composition, and alkali-reactive composition, a method for forming a polymer pattern using the alkali-reactive composition, and the use of the alkali-reactive composition. The method for producing a polymer molded article of a substance is a subject. In order to solve this problem, the present inventors completed the present invention after carefully discussing the results. That is, the present invention provides an alkali-proliferative prepolymer that generates a base upon the action of a base represented by the following formula (1).
本紙張尺度適用中國國家標準（CNS〉A4規格（210X297公釐）_ 6 - I—t--^----裝----Ί—--訂 (請先閱讀背面之注意事項再填寫本頁) 583161 Α7 Β7 經濟部智慧財產局員工消費合作社印製 五、發明説明（4 ) (式中，Ri、R2代表氫原子或甲基、R3、R4代表 其哈曼特取代基定數a m之總和爲0 . 0 5之取代基、R 5 代表二價有機殘基、R6代表η價有機殘基、η代表2〜4 之整數）。 又，本發明係提供一種由該鹼增殖性預聚物與鹼產生 劑所組成者爲特徵之鹼增殖性預聚物組成物者。 本發明更提供一種由該鹼增殖性預聚物、鹼產生劑及 鹼反應性物質所組成者爲特徵之鹼反應性組成物。 本發明更又提供一種由該鹼增殖性預聚物、光鹼產生 劑及聚合性環氧化合物所成之感光性組成物。 本發明更提供以該感光性組成物做爲圖案形成材料使 用爲特徵之圖案形成方法。 本發明又提供於該感光性組成物使活性能量線照射呈 圖案狀後，進行加熱處理者爲特徵之高分子圖案之形成方 法。 本發明更提供該感光性組成物所成成型品中照射活性 能量線後，施予加熱處理者爲特徵之高分子成型品的製造 方法。 本發明之該一般式（1 )鹼增殖性預聚物係藉由鹼觸 媒反應後分解之後，產生做爲具有新穎觸媒能鹼之1級胺 ，此做爲新穎觸媒之機能後，產生增殖性多數胺，由具有 尿烷結合之預聚物所成者。 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 583161 A7 B7五、發明説明（5 ) 某種尿烷衍生物藉由加熱被分解者爲公知者。如：苯 酚類之酸性度其較高之芳香族氫氧基與異氰酸酯所成之尿 烷係經熱分解後使異氰酸酯進行再生者。且，脂肪族醇所 成之某種尿烷衍生物經熱分解後產生胺者亦爲公知者（特 開平11 — 269138號公報）。本發明尿烷衍生物之 特徵爲鹼存在下引起分解者，其結果引起自體觸媒性鹼增 殖反應與先行尿烷衍生物熱分解反應之本質爲相異者。該 鹼增殖反應係結合於該一般式（1 )中R 3及R 4所結合之 碳的氫原子藉由鹼作用後取出，接著脫離胺基甲酸後，此 更分解產生鹼與二氧化碳。其中其所產生鹼再次由尿烷衍 生物取出氫原子後，促進增殖反應，最後引起如下之反應 1—1 ϋ— I >1^ n —-ϋ mi m . ϋϋ ϋ_ι «n in Γϋ 1 h - ^ (請先閲讀背面之注意事項再填寫本頁)This paper size applies to Chinese national standards (CNS> A4 specification (210X297 mm) _ 6-I—t-^ ---- 装 ---- Ί ——-- Order (please read the notes on the back before filling in This page) 583161 Α7 Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (4) (where Ri and R2 represent hydrogen atoms or methyl groups, and R3 and R4 represent their Hammant substituent constants am The sum of the substituents is 0.05, R 5 represents a divalent organic residue, R 6 represents an η-valent organic residue, and η represents an integer of 2 to 4.) In addition, the present invention provides a proliferative property of the base. An alkali-proliferative prepolymer composition characterized by a polymer and an alkali-generating agent. The present invention further provides an alkali-proliferative prepolymer, an alkali-generating agent, and an alkali-reactive substance. Alkali-reactive composition. The present invention further provides a photosensitive composition made of the alkali-proliferative prepolymer, a photo-alkali generator, and a polymerizable epoxy compound. The present invention further provides the photosensitive composition. A pattern forming method is used as a pattern forming material. The present invention also provides After the photoactive composition irradiates the active energy ray into a pattern, a method of forming a polymer pattern characterized by a heat treatment is performed. The present invention further provides an application of the active energy ray after irradiation with the active energy ray in a molded product made of the photosensitive composition. A method for producing a polymer molded product characterized by heat treatment. The general formula (1) of the present invention is a base-proliferative prepolymer which is decomposed after being reacted by an alkali catalyst, and is produced as a base having a novel catalytic energy. Grade 1 amine, which acts as a novel catalyst, produces most amines that are proliferative and are made of prepolymers with urethane binding. (Please read the precautions on the back before filling this page) This paper size applies China National Standard (CNS) A4 specification (210 × 297 mm) 583161 A7 B7 V. Description of the invention (5) A urethane derivative is known by being decomposed by heating. For example, the acidity of phenols is higher. The urethanes formed by aromatic hydroxyl groups and isocyanates are thermally decomposed to regenerate isocyanates. In addition, it is also known that urethane derivatives of aliphatic alcohols generate amines after thermal decomposition (specifically, Kaiping 11-269138). The urethane derivative of the present invention is characterized by being decomposed in the presence of a base, and as a result, the nature of the autocatalytic base proliferation reaction and the thermal decomposition reaction of the prior urethane derivative are different. The alkaline proliferation reaction is based on the hydrogen atoms of the carbons bound to R 3 and R 4 in the general formula (1) are taken out by the action of the base, and then after the amino acid is released, the base and carbon dioxide are decomposed to generate the base and carbon dioxide. After taking out the hydrogen atom from the urethane derivative again, the generated base promotes the proliferation reaction, and finally causes the following reaction 1-1 ϋ— I > 1 ^ n —-ϋ mi m. Ϋϋ ϋ_ι «n in Γϋ 1 h- ^ (Please read the notes on the back before filling this page)
η (1) k I3 I1 --^ Π C + I I λ 4 經濟部智慧財產局員工消費合作社印製η (1) k I3 I1-^ Π C + I I λ 4 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs
(2) 製造本發明鹼增殖性預聚物時，首先，反應下記一般 式（4 ) 0CN-R5-NC0 (4) 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） _ 8 - 583161 Α7 Β7 五、發明説明（6 ) (式中，R5爲與上述意義相同者） 所代表之二異氰酸酯與下記一般式（5 ) H —0 (5) (式中，R6及η爲與上述意義相同者） 所代表之多價醇。藉此反應取得下記一般式（6 ) Η ocn-r5-nx .0(2) When manufacturing the alkali-proliferative prepolymer of the present invention, firstly, the general formula (4) 0CN-R5-NC0 is described below. (4) The paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm). _ 8-583161 Α7 Β7 V. Description of the invention (6) (where R5 is the same as the above meaning) The diisocyanate represented by the general formula (5) H — 0 (5) (where R6 and η Is the same as above). This reaction yields the following general formula (6) Η ocn-r5-nx .0
Y ο R, (6) (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 所代表之具異氰酸酯之尿院衍生物者。 該二異氰酸酯與多價醇相互之反應係藉由公知方法使 異氰酸酯基與氫氧基呈等莫耳量兩成份進行混合之，於觸 媒之存在下或不存在下進行反應即可。 再於該一般式（6)之化合物中使下記一般式（7) I I . H — C — C — OH (7)Y ο R, (6) (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, which represents a urine urine derivative with isocyanate. The reaction between the diisocyanate and the polyvalent alcohol is carried out by mixing the isocyanate group and the hydroxyl group at equal molar amounts by a known method, and the reaction may be performed in the presence or absence of a catalyst. Then, in the compound of the general formula (6), the following general formula (7) I I. H — C — C — OH (7)
I I Κ·4 R2 (式中，Ri、R2、R3、R4爲與上述意義相同者） 所代表之醇反應其異氰酸酯基即可。此時爲促進異氰 酸酯與醇基相互之反應，其慣用之尿烷形成用觸媒爲適用 者。 該一般式（4) 、R5代表2價有機基、而此2價有 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐） -9 - 583161 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（7 ) 機基中包含2價脂肪族基及2價芳香族基。2價脂肪族基 中其碳數爲2〜2 0者，較佳者爲3〜14。2價脂肪族 基中，包含鏈狀及環狀者。鏈狀中包含伸烷基及伸烯者， 而，理想之鏈狀脂肪族基爲碳數3〜1 〇者，較佳者爲4 〜8之亞烷基者。2價環狀脂肪族基中，包含具碳數5〜 2 0者，較佳者爲6〜1 0之脂肪族環者。 該脂肪族基中，亦可結合取代基者。此時之取代基對 於該反應爲不活性者。此取代基包含鹵原子、碳數1〜6 之烷氧基，碳數1〜6之烷氧基羰基，碳數1〜6之醯基 等。又，鏈狀脂肪基係於其主鏈中含氧原子、氮原子、硫 原子等雜原子亦無妨。 該2價芳香族基中，其芳香環包含碳環或複環所成者 。又，其碳環所成芳香族基中包含單獨（苯環）、縮合多 環（萘環、嵌二萘環、甘菊環、芴環、蒽環、®環等）及 鏈狀多環（聯苯環、聯三苯環等）。複環所成之芳香族基 係至少1個含氮原子、氧原子、硫原子等雜原子之雜芳香 族基者。 此芳香族基中，其環構成原子數爲4〜2 0，較佳爲 5〜1 0者。做爲該複環例者如：噻吩環、苯並噻吩環、 噻嗯環、呋喃環、苯並呋喃環、咔唑環、吡啶環、哌啶環 、吡咯烷環等例。 該2價芳香族基中，亦可結合取代基。此時之取代基 對於該反應爲不活性者。此取代基包含鹵原子、碳數1〜 6之烷基、碳數1〜6之烷氧基、苯基、萘基等。 本紙張尺度適用中國國家標準（CNS ) A4規格（210χ297公羡) ' — II--^----v裝----Ί--訂------,/1 (請先閱讀背面之注意事項再填寫本頁) 583161 Α7 __ Β7 經濟部智慧財產局員工消費合作社印製 五、發明説明（8 ) 做爲該二異氰酸酯之具體例者如：先行各種公知者， 如：六亞甲基二異氰酸酯、異氟爾酮二異氰酸酯、甲苯燒 二異氰酸酯等例。 該一般式（5)所示之多價醇中，R6代表η (n = 2 〜4 )價之有機基，而，此時之n價有機基包含η價脂肪 族基及芳香族基。η價脂肪族基中其碳數爲2〜1 6，較 佳爲2〜1 0者。此η價脂肪族中包含鏈狀及環狀者。又 ’鏈狀之脂肪族基時，其主鏈中亦可含有氧原子、氮原子 、硫原子等雜原子。 該脂肪族基中亦可結合取代基。此時取代基對於該反 應爲不活性者。此取代基中包含鹵原子、碳數1〜6之烷 氧基、碳數1〜6之烷氧基羰基、，碳數1〜6之醯基等。 該η價芳香族基中，其芳香環包含碳環或複環所成者 。又，由其碳環所成之芳香族基中包含單獨（苯環）、縮 合多環（萘環、嵌一萘環、甘菊環、苟環、蒽環、雇環等 )及鏈狀多環（聯苯環、聯三苯環等）。由複環所成之芳 香族基係至少1個含氮原子、氧原子、硫原子等雜原子之 雜芳香族基者。 該η價芳香族基中，亦可結合取代基。此時之取代基 對於反應爲不活性者。此取代基中包含鹵原子，碳數1〜 6院基、碳數1〜6之烷氧基、碳數1〜6之烷氧基羰基 、碳數1〜6之醯基、苯基、萘基等。 做爲該多價醇之例者有先行各種公知者，如：乙二醇 、丙二醇、丁二醇、二乙二醇、三乙二醇、聚乙二醇、丙 $-- (請先閲讀背面之注意事項再填寫本頁) ，τ 本紙張尺度適用中國國家標準（CNS )八4規格（210Χ297公釐） 583161 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（9 ) 二二醇、二丙二醇、聚丙二醇、甘油、二甘油、糖醇（赤 蘚醇、木糖醇、季戊四醇等）等例。 該一般式（7 )所示醇中，其取代基R 3及R 4係對應 該一般式（1 )鹼增殖性預聚物中之取代基R 3及R 4者。 該鹼增殖性預聚物中結合於其取代基R 3及R 4所結合之碳 (以下稱位碳）的氫原子（以下稱/5位氫原子）被要求 於鹼之存在下做爲質子進行脫離者。因此，該一般式（7 )所示之醇中取代基R3、R 4選定對應此要求者爲極重要 者。 該一般式（1 )之鹼增殖性預聚物中鹼存在下之/5位 氫之脫離反應係藉由Θ位碳之酸性度與鹼之鹼性而決定者 〇 /3位碳之酸性度係具有弱電子吸引能之尿烷性殘基之 同時藉由Rl、R2、R3及R4之取代基效果而定。由與異 氰酸酯基之反應性及醇的安定性而視之，R i及R 2爲氫原 子或甲基者宜。因此，R 3及R 4務必至少任一爲電子吸引 性取代基者，且，爲促進Θ位氫的脫離反應，期待所生成 之烯烴化合物之雙鍵呈電子共軛者。 電子吸引性係以醋酸之酸解離定數爲基準所使用經驗 的數値可以哈曼特之取代基定數（am)表示之。/3位碳 係以尿烷基、R 3及R 4所取代者，其酸性度分別決定其取 代基定數。通常，取代基效果幾乎以取代基定數之總和表 示之，該一般式（7 )之醇中，只考量Rs及R4之取代基 定數之和即可。做爲附與本發明一般式（7 )所示之鹼增 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） _ 12 - 583161The alcohol represented by I I κ · 4 R2 (wherein Ri, R2, R3, and R4 have the same meanings as described above) may react with their isocyanate groups. In this case, in order to promote the mutual reaction between isocyanate and alcohol group, a conventional catalyst for urethane formation is suitable. The general formula (4) and R5 represent a bivalent organic group, and this bivalent has the paper size applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -9-583161 A7 B7 Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the consumer cooperative V. Description of the invention (7) The machine base contains a divalent aliphatic group and a divalent aromatic group. The divalent aliphatic group has 2 to 20 carbon atoms, preferably 3 to 14. The divalent aliphatic group includes those having a chain shape and a cyclic shape. Those having an alkylene group and an alkylene group in a chain form, and the ideal chain aliphatic group is one having a carbon number of 3 to 10, more preferably an alkylene group having 4 to 8 carbon atoms. The divalent cyclic aliphatic group includes those having 5 to 20 carbon atoms, more preferably 6 to 10 aliphatic rings. The aliphatic group may be substituted with a substituent. The substituent at this time is inactive for the reaction. This substituent includes a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, a fluorenyl group having 1 to 6 carbon atoms, and the like. In addition, the chain fatty group may be a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom in its main chain. In the divalent aromatic group, the aromatic ring includes a carbon ring or a complex ring. The aromatic group formed by the carbocyclic ring includes a single (benzene ring), a condensed polycyclic ring (naphthalene ring, perylene ring, chamomile ring, pyrene ring, anthracene ring, ® ring, etc.) and a chain polycyclic ring (biphenyl ring). Ring, bitriphenyl ring, etc.). The aromatic group formed by the complex ring is a heteroaromatic group containing at least one hetero atom such as a nitrogen atom, an oxygen atom, and a sulfur atom. In this aromatic group, the number of ring constituent atoms is 4 to 20, preferably 5 to 10. Examples of the complex ring include thiophene ring, benzothiophene ring, thion ring, furan ring, benzofuran ring, carbazole ring, pyridine ring, piperidine ring, and pyrrolidine ring. A substituent may be bonded to the divalent aromatic group. The substituent at this time is inactive for the reaction. This substituent includes a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a naphthyl group, and the like. This paper size applies to China National Standard (CNS) A4 specification (210 × 297 public envy) '— II-^ ---- v equipment ---- Ί--order ------, / 1 (Please read first Note on the back, please fill out this page again) 583161 Α7 __ Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (8) As specific examples of the diisocyanate, for example, the various publicly known persons, such as: Examples are methyl diisocyanate, isoflurone diisocyanate, and toluene diisocyanate. In the polyvalent alcohol represented by the general formula (5), R6 represents an organic group of η (n = 2 to 4) valence, and the n-valent organic group at this time includes an η-valent aliphatic group and an aromatic group. The carbon number of the η-valent aliphatic group is 2 to 16 and more preferably 2 to 10. The η-valent aliphatic includes chain-like and cyclic ones. In the case of a chain-like aliphatic group, the main chain may contain hetero atoms such as an oxygen atom, a nitrogen atom, and a sulfur atom. A substituent may be bonded to the aliphatic group. At this time, the substituent is inactive to the reaction. The substituent includes a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, a fluorenyl group having 1 to 6 carbon atoms, and the like. In the n-valent aromatic group, the aromatic ring includes a carbocyclic ring or a complex ring. In addition, the aromatic group formed by the carbocyclic ring includes a single (benzene ring), a condensed polycyclic ring (naphthalene ring, a naphthalene ring, a camomile ring, a Gou ring, an anthracene ring, a ring, etc.) and a chain polycyclic ring Biphenyl ring, bitriphenyl ring, etc.). The aromatic aromatic group formed by a complex ring is a heteroaromatic group containing at least one hetero atom such as a nitrogen atom, an oxygen atom, and a sulfur atom. A substituent may be bonded to the n-valent aromatic group. Substituents at this time are inactive to the reaction. This substituent contains a halogen atom, 1 to 6 carbons, alkoxy 1 to 6 carbons, alkoxy carbonyl 1 to 6 carbons, fluorenyl 1 to 6 carbons, phenyl, naphthalene Base etc. As examples of the polyvalent alcohol, there are various publicly known ones, such as ethylene glycol, propylene glycol, butanediol, diethylene glycol, triethylene glycol, polyethylene glycol, and propylene. (Please read first Note on the back, please fill in this page again), τ This paper size is applicable to China National Standard (CNS) 8-4 specifications (210 × 297 mm) 583161 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (9) 2 Examples of glycols, dipropylene glycol, polypropylene glycol, glycerol, diglycerin, sugar alcohols (erythritol, xylitol, pentaerythritol, etc.). In the alcohol represented by the general formula (7), the substituents R 3 and R 4 correspond to those of the substituents R 3 and R 4 in the base multiplyable prepolymer of the general formula (1). In the alkali-proliferative prepolymer, a hydrogen atom (hereinafter referred to as a / 5-position hydrogen atom) bound to a carbon (hereinafter referred to as a position carbon) bound to its substituents R 3 and R 4 is required to be used as a proton in the presence of a base. Carry out. Therefore, it is extremely important that the substituents R3 and R4 in the alcohol represented by the general formula (7) be selected to correspond to this requirement. In the alkali-proliferative prepolymer of the general formula (1), the / 5-position hydrogen release reaction in the presence of a base is determined by the acidity of the carbon at Θ and the basicity of the base. It is a urethane residue having a weak electron attraction, and it is determined by the effect of the substituents of R1, R2, R3, and R4. In view of its reactivity with isocyanate groups and the stability of alcohols, R i and R 2 are preferably hydrogen atoms or methyl groups. Therefore, at least one of R 3 and R 4 must be an electron-attracting substituent, and in order to promote the detachment reaction of the hydrogen at the Θ position, it is expected that the double bond of the olefin compound to be formed is electron-conjugated. Electron attractivity is a number based on the empirical value of the acid dissociation constant of acetic acid. It can be expressed by the Hammant substituent number (am). The / 3-position carbon is substituted by urethane, R 3 and R 4 and its acidity determines its substitution number. In general, the effect of substituents is almost expressed by the sum of the substituent numbers. In the alcohol of the general formula (7), only the sum of the substituent numbers of Rs and R4 can be considered. As the alkali increase shown in the general formula (7) of the present invention (please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) _ 12-583161
(1 ) HOCH2CH2-CN A7 B7 五、發明説明（10) 殖性預聚物之醇取代基者其R 3及R 4取代基定數σ m之總 和爲+0.01〜+0·7者宜，較佳者爲0.02〜 0 · 0 6。當小於此範圍時，則/3位碳之酸性度變小，而 藉由加熱造成分解反應，而無法有效引起鹼增殖反應。另 外，超出此範圍時，即使無鹼存在下仍容易自發性分解呈 不安定者。 做爲附與本發明理想之鹼增殖性預聚物之電子吸引性 ，且，可與烯烴性雙鍵共軛之取代基例者如：乙烯基、苯 基、取代苯基、芳香族性複環殘基（噻嗯基、吡啶基 '呋 喃基、嘧啶基等）、氰基、酮性羰基、酯性羰基、醯胺性 羰基、尿烷性羰基、亞碼基等例。又’做爲此等取代基之 構成要因者亦訂R 3、R 4結合後形成環者。‘‘如‘ ：R 3與R 4 結合後呈芴基、茚滿基等者。 做爲該一般式（7 )所示醇之具體例者如以下示例者 ch3(1) HOCH2CH2-CN A7 B7 V. Description of the invention (10) The alcohol substituents of the colony prepolymer whose R 3 and R 4 substituent constants σ m are preferably + 0.01 ~ + 0 · 7, The preferred value is 0.02 to 0 · 0 6. When it is smaller than this range, the acidity of the / 3-position carbon becomes small, and the decomposition reaction is caused by heating, and the alkali proliferation reaction cannot be effectively caused. In addition, if it exceeds this range, it is easy to spontaneously decompose even in the absence of alkali. Examples of substituents that can be conjugated with olefinic double bonds as electron attractors that are ideally attached to the base-proliferating prepolymer of the present invention include vinyl, phenyl, substituted phenyl, and aromatic compounds. Examples of ring residues (thienyl, pyridyl'furanyl, pyrimidinyl, etc.), cyano, keto-based carbonyl, ester-based carbonyl, amido-based carbonyl, urethane-based carbonyl, and methylene. Also, as a constituent of these substituents, R 3 and R 4 are combined to form a ring. ‘‘ Such as ’: R 3 and R 4 are combined with fluorenyl, indanyl, and the like. Specific examples of the alcohol represented by the general formula (7) are as follows: ch3
(12) HO—i—CH2—CM (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 (2) hoch2ch2-coch3 (3) H0CH2CH2-C02CH3 uri ^ 2 (13) HO——CH——CHa—C02CH2—^ (4 ) H0CH2CH2—C02CH2—* 〇 (14) H〇CH2CH2-S02-^ \ (5 ) H0CH2CH^S0CH3 ^’ CH3 CHa Ο 13- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 583161 A7 B7 ?h2 五、發明説明（11) H0、 (6) H0CH2CH2-S02CHa (15) CHa l T CH3 (7) hoch2ch2—conh2 (8 ) H〇CH2CH2~^(12) HO—i—CH2—CM (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (2) hoch2ch2-coch3 (3) H0CH2CH2-C02CH3 uri ^ 2 (13 ) HO——CH——CHa—C02CH2— ^ (4) H0CH2CH2—C02CH2— * 〇 (14) H〇CH2CH2-S02- ^ \ (5) H0CH2CH ^ S0CH3 ^ 'CH3 CHa 〇 13- This paper size applies to China National standard (CNS) A4 specification (210X297 mm) 583161 A7 B7? H2 V. Description of the invention (11) H0, (6) H0CH2CH2-S02CHa (15) CHa l T CH3 (7) hoch2ch2-conh2 (8) H. CH2CH2 ~ ^
N HO. (9) CH3 HOCHCH2—CO2CH3 CH2 (10) 9 (17) H0-CH2CH2CF2CF2CF2CF3 hochch2—co2ch3 (11) HOGhIa — GH,N HO. (9) CH3 HOCHCH2—CO2CH3 CH2 (10) 9 (17) H0-CH2CH2CF2CF2CF2CF3 hochch2—co2ch3 (11) HOGhIa — GH,
(18) HOCH2—He(18) HOCH2--He
(請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本發明鹼增殖性預聚物組成物係含有鹼增殖性預聚物 及鹼產生劑之組成物者。此組成物可爲液狀或固狀者。 鹼產生劑中包含加熱後產生鹼、照射活性能線（光、 X線等電磁波、電子線等）產生鹼者等。此鹼產生劑有先 行公知者，可使用各種公知者。如：做爲藉由光作用產生 鹼之鹼產生劑例可使用利用於化學增幅型光致抗蝕劑（有 機電子學材料硏究會編，「影像用有機材料」、文心出版 (1993年）。又，爲擴大此等光鹼產生劑之感光波長 領域，亦可共存適當光增感劑。此等物質藉由光分解產生 之鹼作用於鹼增殖性預聚物後，促進鹼之產生。以下代表 本發明之理想光鹼產生劑之示例。 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -14- 583161 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（12) CHa ，C 一。一M^C、 b (2) ch3(Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The alkali-proliferative prepolymer composition of the present invention is a composition containing an alkali-proliferative prepolymer and an alkali generator. This composition may be liquid or solid. The alkali generating agent includes those which generate alkali upon heating and irradiate active energy rays (electromagnetic waves such as light and X rays, electron rays, etc.) to generate alkali. The alkali generating agent is known in advance, and various known ones can be used. For example, as an example of an alkali generating agent that generates alkali by the action of light, it can be used in chemically amplified photoresists (edited by the Organic Electronics Materials Research Society, "Organic Materials for Imaging", Wenxin Publishing (1993) ). In addition, in order to expand the photosensitive wavelength range of these photo-alkali generators, appropriate photo-sensitizers can also be co-existed. After these substances act on the alkali-proliferative prepolymer through the base generated by photodecomposition, they promote the production of alkali. The following represents an example of the ideal photo-alkali generator of the present invention. This paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) -14- 583161 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 、 Explanation of the invention (12) CHa, C a. One M ^ C, b (2) ch3
C-Q-M=C ⑴C-Q-M = C ⑴
H3Wo -C-*CH2CHz-C-Q-H=CiN 0 1 ' (4) CHaH3Wo -C- * CH2CHz-C-Q-H = CiN 0 1 '(4) CHa
.〇-^=C.〇-^ = C
H G ,CH3 3 b=N-〇-C-CH2CHr-C-0~N=C (請先閱讀背面之注意事項再填寫本頁) ΟH G, CH3 3 b = N-〇-C-CH2CHr-C-0 ~ N = C (Please read the precautions on the back before filling this page) Ο
(5) (6) CHa CH3 CH3 H3C-C—C-O-N^C όΗ3δ b(7) 十CH彳H^CH彳今c=o ac 、CHa (9) d 8 6" b(8) 十 CH2CH^-(CHf 丨)- r=n C-0 c=a \ o a 6h2CH3 ca 、CHa (10) 本紙張尺度適用中國國家標準（CNS ) A4規格（21 OX 297公釐） -15 - 583161 A7 B7 五、發明説明（13)(5) (6) CHa CH3 CH3 H3C-C—CON ^ C ό3δ b (7) Ten CH 彳 H ^ CH 彳 present c = o ac, CHa (9) d 8 6 " b (8) Ten CH2CH ^- (CHf 丨)-r = n C-0 c = a \ oa 6h2CH3 ca 、 CHa (10) This paper size is applicable to Chinese National Standard (CNS) A4 (21 OX 297 mm) -15-583161 A7 B7 V. Invention Description (13)
12) I3C1 H3312) I3C1 H33
13 ca Ί13 ca Ί
Ha HaZG s ♦Ha HaZG s ♦
14) 151 /fv14) 151 / fv
1717
19 (請先閲讀背面之注意事項再填寫本頁) -裝- 訂 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -16 - 583161 A7 B7 五、發明説明（Η) 經濟部智慧財產局員工消費合作社印製19 (Please read the precautions on the back before filling out this page)-Binding-Order the paper printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, the Consumer Cooperatives. The paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm) -16-583161 A7 B7 V. Description of Invention (Η) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs
I ~% ^ '裝 ^ 訂 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -17 - 583161 A7 B7 五、發明説明（15)I ~% ^ 'binding ^ binding (please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 specification (210 × 297 mm) -17-583161 A7 B7 V. Description of the invention (15 )
HacqHacq
HaC〇HaC〇
?η3 (31)? η3 (31)
C*^NH2 och3HqC〇 (34) (33)C * ^ NH2 och3HqC〇 (34) (33)
(35) OCHa ^ 3 C)CHa (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -18 - 583161 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（16) N〇2(35) OCHa ^ 3 C) CHa (Please read the notes on the back before filling out this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Employee Consumer Cooperatives This paper is printed in accordance with Chinese National Standard (CNS) A4 (210X297 mm)- 18-583161 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy V. Invention Description (16) N〇2
βχΟ (41) CHa NO,, (43) NO,βχΟ (41) CHa NO ,, (43) NO,
N〇i4rr3 CH3 (4Z)No.i4rr3 CH3 (4Z)
N〇2 (44) N〇a 电。(45) ⑽No2 (44) Noa electricity. (45) ⑽
NO^ OaNNO ^ OaN
«-ΝΗ- 6(47)«-ΝΗ- 6 (47)
HaCO-HaCO-
(請先閲讀背面之注意事項再填寫本頁) Ν〇ι "(Please read the notes on the back before filling this page) Ν〇ι "
n〇2 CHi"-〇-C-NH NOo N〇2 0-an〇2 CHi " -〇-C-NH NOo N〇2 0-a
(49)(49)
O^N 〇aN(50) OJ N〇2 · (51)O ^ N 〇aN (50) OJ No〇2 (51)
)-C-N °Λ (52) N〇2 N〇i -CH2CH2CVVH^^N1,〇"^Hzc) -C-N ° Λ (52) No 〇2 No 〇i -CH2CH2CVVH ^^ N1, 〇 " ^ Hzc
(53)(53)
O2N 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -19 - 583161 A7 B7 [CoiNHJsBfl (CI〇4)2 (61) 五、發明説明（17) 0 °s (62) (63) (64) 該No. (1)〜（10)之化合物爲肟脂系化合物 者，藉由光作用產生席夫鹼，藉由此水解後產生胺。其中 ，Νο· (9)及No . (10)之化合物爲高分子化合 物者，對於該高分子側鏈照射光後，產生胺。O2N This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) -19-583161 A7 B7 [CoiNHJsBfl (CI〇4) 2 (61) 5. Description of the invention (17) 0 ° s (62) (63 ) (64) The compounds of Nos. (1) to (10) are oxime lipid compounds, which generate a Schiff base by the action of light, and thereby generate an amine by hydrolysis. Among them, the compounds of No. (9) and No. (10) are polymer compounds, and the polymer side chains are irradiated with light to generate amines.
No. (11)〜（19)之化合物爲胺系化合物者 ，藉由光分解產生三級胺。The compounds of Nos. (11) to (19) are amine compounds, and tertiary amines are generated by photolysis.
No. (2 1)〜（28)之化合物爲苯偶因系化合 物者，藉由光分解後，產生胺。The compounds of Nos. (2 1) to (28) are benzoin-based compounds, and amines are generated by photodecomposition.
No. (3 1)〜（3 5)之化合物係二甲氧基苄尿 烷系化合物者，藉由光分解後產生胺。The compounds of No. (3 1) to (3 5) are dimethoxybenzylurethane-based compounds, and amines are generated by photodecomposition.
No. (41)〜（53)之化合物爲鄰硝苄尿烷系 化合物者，藉由光分解後產生胺。The compounds of Nos. (41) to (53) are o-nitrobenzylurethane-based compounds, and amines are generated by photodecomposition.
No. (61)〜（64)代表其他之光鹼產生劑。 N 〇 ·( 6 1 )之化合物係藉由光照射後以氨爲產生 之鹼。 ~7‘ •裝 ^ *訂 次 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X297公釐） 20 583161 A7 ____ B7 五、發明説明（18)Nos. (61) to (64) represent other photobase generators. A compound of No. (6 1) is a base produced by ammonia after irradiation with light. ~ 7 '• Packing ^ * Order (please read the notes on the back before filling this page) Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper applies the Chinese National Standard (CNS) A4 specification (210 X297 mm) 20 583161 A7 ____ B7 V. Description of the invention (18)
No. ( 6 2 )之化合物係藉由光照射後，以過氧化 物離子爲產生之鹼。N 〇 ·( 6 3 )之化合物係藉由光照 射後，以胺做爲產生之鹼。No.(64)之化合物係藉 由光照射後，以胺爲產生之鹼。 做爲加熱產生鹼之化合物例者如以下所示者。 1.1111 I n * ΐ衣 n Ί— 訂 I I ^ ·*w (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS〉A4規格（210X297公釐） -21 - 583161 A7 B7 五、發明説明（19) (ε α9)The compound of No. (6 2) is a base generated by peroxide ion after irradiation with light. A compound of No. (63) is a base produced by amine irradiation after light irradiation. The compound of No. (64) is a base produced by amine after irradiation with light. Examples of compounds that generate a base upon heating are shown below. 1.1111 I n * ΐ 衣 n Ί — Order II ^ · * w (Please read the precautions on the back before filling out this page) Printed on the paper by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs. The paper size applies to Chinese national standards (CNS> A4 specifications) (210X297 mm) -21-583161 A7 B7 V. Description of the invention (19) (ε α9)
2£—OIOOWTU 十2 £ —OIOOWTU Ten
X,、 宴IV hfJOof + 經濟部智慧財產局員工消費合作社印製 κν— (s) on .Η foi8f0X ,, Banquet IV hfJOof + Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs κν— (s) on .Η foi8f0
(S) ΘΗ2 十(S) ΘΗ2 十
(6 卜)<mh2 +(6 b) < mh2 +
NWH —ο"ϋ£88Ι"ϋ?NWH —ο " ϋ £ 88Ι " ϋ?
--:----'裝-- (請先閲讀背面之注意事項再填寫本頁) *11 sooalozo ^sx'oscsl +?x丨ο'ΟΝΗοοοοεΗαοι 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -22 - 583161 A7 B7 五、發明説明（20) 本發明含鹼增殖性預聚物與鹼產 物組成物中，其鹼產生劑之比例並無 對鹼增殖性預聚物於重量比以1〜1 佳者爲5〜40重量％者。 該鹼增殖性預聚物組成物係藉由 殖性產生其鹼者。此組成物係將此配 後，使其鹼反應性質之反應藉由加熱 之。 本發明鹼反應性組成物爲含有鹼 性預聚物及鹼產生劑之組成物者。此 狀者。 鹼反應性物質中包含1種或2種 分解反應、脫離反應、縮合反應、聚 化學物質者。此化學物質可爲低分子 子物質（聚合物）等者。 鹼反應性物質可爲被鹼觸媒反應 之高分子物質者，且，藉由鹼觸媒後 樹脂組成物或聚合物者。其例如下。 生劑之鹼增殖性預聚 特別限定，一般，針 00重量％者宜，較 熱、光等作用後，增 合各種鹼反應性物質 、光照射後開始進行 反應性物質、鹼增殖 組成物可爲液狀或固 以上藉由鹼作用產生 合反應等化學反應之 物質、低聚物、高分 所引起之殘基所取代 之縮合反應所代表之 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製-: ---- 'Installation-(Please read the precautions on the back before filling in this page) * 11 sooalozo ^ sx'oscsl +? X 丨 ο'ΟΝΗοοοοεΗαοι This paper standard applies to China National Standard (CNS) A4 specifications (210X297 mm) -22-583161 A7 B7 V. Description of the invention (20) The proportion of the alkali generating agent in the alkali-proliferating prepolymer and the alkali product composition of the present invention is not as high as that of the alkali-proliferating prepolymer. A weight ratio of 1 to 1 is preferably 5 to 40% by weight. This alkali-proliferative prepolymer composition is one which produces its base by colonization. This composition is prepared by heating and reacting the base with a reaction property. The alkali-reactive composition of the present invention is a composition containing an alkali-based prepolymer and an alkali generator. This is the case. The alkali-reactive substance includes one or two kinds of decomposition reactions, desorption reactions, condensation reactions, and polymer chemicals. This chemical substance may be a low molecular substance (polymer) and the like. The alkali-reactive substance may be a polymer substance that is reacted by an alkali catalyst, and a resin composition or a polymer after the alkali catalyst. Its example is as follows. The alkali-proliferative prepolymerization of the biological agent is particularly limited. Generally, 00% by weight is preferred. After the action of heat and light, various alkali-reactive substances are added, and the reactive substances and alkali-proliferation composition may be started after light irradiation. It is represented by the condensation reaction that is replaced by residues caused by chemical reaction such as liquid or solid by the action of alkali, oligomers, and high scores (please read the precautions on the back before filling this page) ) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs
〇-C-0-C-.CH2-CN 〇 CHa ch3〇-C-0-C-.CH2-CN 〇 CHa ch3
〇—r〇fCHirS〇rO (81) 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐）-23 - 583161 A7 B7 五、發明説明（21)〇—r〇fCHirS〇rO (81) This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) -23-583161 A7 B7 V. Description of the invention (21)
CH3 (82) ch3CH3 (82) ch3
(87) (請先閲讀背面之注意事項再填寫本頁)(87) (Please read the notes on the back before filling this page)
l^C02H CMl ^ C02H CM
經濟部智慧財產局員工消費合作社印製 (88) 該 N 0 · ( 8 0 ) N 〇 . (80)〜（83)之化合物係藉由鹼作用後’產 生脫離及脫碳酸反應。No· (84)〜（85)之化合 物係藉由驗作用產生脫碳酸反應。 該No · (86)〜（89)之鹼反應性物質中，N 〇 · (86)之物質（混合物）係藉由鹼作用後產生脫水 縮合及交聯反應者。No ·( 8 7)之物質（混合物）係 本紙張尺度適用中國國家標準（CNS )八4規格（210 X 297公釐）-24 583161 A7 B7 五、發明説明（22) 藉由鹼作用後產生脫水縮合及交聯反應者。No. (88 )之物質（聚合物）係藉由鹼作用後，產生脫碳酸反應者 。N 〇 · ( 8 9 )之物質係藉由鹼作用後，產生亞胺形成 之反應。 鹼反應性物質可具有至少2個環氧基之物質者。於至 少具有2個環氧基化合物藉由鹼（胺）之作用後，可使其 環氧化合物藉由其環氧基之開環聚合做成聚合物。且，於 環氧化合物中使胺藉由附加反應後，可使其環氧化合物進 行化學變性。 以下代表聚合反應性所示之環氧化合物具體例者。 (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (88) The N 0 · (80) N 〇. (80) ~ (83) compounds are detached and decarbonated by the action of alkali. The compounds of No. (84) to (85) produce decarbonation reaction by inspection. Among the alkali-reactive substances of No. (86) to (89), the substance (mixture) of No. (86) is a substance that generates dehydration condensation and cross-linking reaction by the action of a base. No. (8 7) The substance (mixture) is the size of this paper applicable to the Chinese National Standard (CNS) 8 4 specifications (210 X 297 mm) -24 583161 A7 B7 V. Description of the invention (22) Produced by the action of alkali Dehydration condensation and cross-linking reaction. The substance (polymer) of No. (88) is a decarbonated reaction by the action of a base. No. (89) is a substance that reacts with an alkali to form an imine. The base-reactive substance may be one having at least two epoxy groups. After having at least two epoxy compounds through the action of a base (amine), the epoxy compound can be made into a polymer by ring-opening polymerization of its epoxy groups. In addition, after the amine is added to the epoxy compound by an additional reaction, the epoxy compound can be chemically denatured. Specific examples of the epoxy compound represented by the polymerization reactivity are shown below. (Please read the notes on the back before filling this page)
〇 0 〇 (91) ο 經濟部智慧財產局員工消費合作社印製 (92)〇 0 〇 (91) ο Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (92)
(93)(93)
：〇 尽尺度填用中國國家標準（CNS ) ( 210 X 297公釐）-25 583161 A7 B7 Q": 〇 Fill in the Chinese National Standard (CNS) (210 X 297 mm) to the fullest extent. -25 583161 A7 B7 Q "
0 (96) 五、發明説明（23) Η CH3—CH2—C^CH2—〇WH2—q^CH2 ) ' ο 、 (97) 以下代表聚合反應性所示之其他環氧化合物（環氧樹 脂）之例I。0 (96) V. Description of the invention (23) Η CH3-CH2—C ^ CH2—〇WH2—q ^ CH2) 'ο, (97) The following represent other epoxy compounds (epoxy resins) shown by polymerization reactivity Example I.
(98)(98)
V (99)V (99)
該鹼反應性組成物中，鹼反應物質之比例爲1當量鹼 增殖性預聚物中尿烷殘基之〇 · 1〜1 〇當量者宜，較佳 者爲0·4〜5當量，更佳者爲0·5〜3當量者。 該鹼反應性組成物中可添加低分子鹼增殖劑者。做爲 —7 i :: * 批本 j 訂^ (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -26 - 583161 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（24) 低分子鹼增殖劑之例者可使用由一般式（4 )所示之脂肪 族二異氰酸酯與一般式（7 )所示之醇所取得之雙尿烷衍 生物者。此雙尿烷衍生物呈增殖性產生1級胺，藉由此添 加後，可更加速鹼增殖性預聚物之反應，因此，可提昇此 取得樹脂組成物之反應性。 該組成物中必要時可適量添加顏料、二氧化矽粒子等 補助添加成份。 本發明理想之鹼反應性組成物爲含有聚合性環氧化合 物之聚合反應性組成物者。此組成物藉由光或熱作用後， 進行聚合後，附與聚合物。 本發明理想之鹼反應性組成物係藉由光開始聚合反應 之組成物者。此組成物係由聚合性環氧化合物與鹼增殖性 預聚物及光鹼產生劑所成者，必要時可含有低分子鹼增殖 劑、聚合性環氧化合物用硬化劑、硬化促進劑、其他塡充 劑等輔助成份之組成物者。該組成物可有效做爲圖案形成 材料，被膜形成材料之用者。 利用此感光性組成物形成圖案時，如：將此感光性組 成物溶於有機溶媒後，作成塗佈液，將此塗佈液塗佈於基 板等適當之固體表面，進行乾燥後，形成塗膜。針對此塗 膜進行圖案曝光後產生鹼。再進行加熱處理後，促進鹼增 殖性預聚物之連續性分解。加熱處理條件依曝光能，所使 用鹼中活性鹼增殖性預聚物之種類、環氧化合物之種類等 進行變更，一般加熱溫度爲60 °C〜1 50 °C，更佳者爲 8 0 °C〜1 3 0 °C。加熱時間由1 0秒〜1 0分鐘，更佳 ,, :---^-- (請先閲讀背面之注意事項再填寫本頁) 、言 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） _ 27 - 583161 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（25) 者爲3 0秒至5分鐘。將此浸漬於曝光與未曝光部份產生 溶解度差之溶媒中，進行顯像後取得圖案。 利用該感光性組成物形成被膜時，如：將此感光性組 成物溶於有機溶媒後作成塗佈液，此塗佈液塗於基板等適 當之固體表面後，進行乾燥形成塗膜。對於此塗膜照射光 後產生鹼。再進行加熱處理後促進鹼增殖性預聚物之連續 性分解。加熱處理條件依其光能，所使用鹼其活性鹼增殖 預聚物種類、環氧化合物之種類等而變更，而，一般加熱 溫度爲60°C〜1 50°C，更佳者爲80°C〜 1 3 0 °C者。加熱時間爲1 0秒至1 〇分鐘，更佳者爲 3 0秒至5分鐘。如此於固體表面上形成環氧樹脂之硬化 被膜。 該固體表面包含玻璃、塑膠、金屬、陶瓷等。 〔發明效果〕 本發明容易藉由光、熱之作用切斷尿烷結合後，其多 價1級胺於未端產生增殖性之預聚物，因此，與此等反應 之化合物所成之組成物爲感應於熱、光之熱樹脂者。如： 共存環氧化合物後可使其組成物藉由光、熱硬化之。如此 所調製之硬化物其體積收縮小，且粘著性佳，因此，可強 固被覆基板表面。又，藉由呈圖案狀曝光後亦可形成圖案 。因此，藉由本發明組成物可適用於各種紫外線硬化型油 墨、熱硬化性塗料等之製造者。 丨丨^--^----丨裝----：---訂------旅 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -28 - 583161 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（26) 〔實施例〕 以下，藉由實施例詳述本發明。 〔實施例1〕（鹼增殖性低聚物（1 )之合成） 於352之含二月桂酸二—正—丁錫（〇.〇7呈， 0 · lmmo 1 )之脫水苯中加入9 —芴基甲醇（4 . 5 g、23mmo 1 )之溶解溶液後，於氮氣下進行加熱環 流後溶解之。將3 5重量份之聚四亞甲基二醇（分子量 2 0 0 0 )與2當量異氟爾酮二異氰酸酯所調製之異氰酸 酯低聚物- 1、與6 5重量份之新戊二醇與2當量異氟爾 酮二異氰酸酯所調製之異氰酸酯低聚物- 2所成1 5 g混 合物溶於7 0 脫水苯中。將此後者溶液利用滴入漏斗滴 入前者溶液後，於氮氣下攪拌之同時進行加熱迴流4小時 。期間，藉由薄層層析法追踪反應之進行。反應結束後， 減壓餾去溶媒後，取得高粘度之鹼增殖性尿烷低聚物（1 )(2 0 g )。 〔比較例1〕（未具鹼增殖能之圖案低聚物的合成） 以9 —芴醇（4 · 2g，23mmo 1)取代實施例 1所使用之9 一芴基甲醇加入3 5J之含有二月桂酸二一 正—丁錫（0 · 07g、0 . lmmo 1)之脫水苯中之 後，於氮氣下進行加熱迴流溶解之。於該溶液中利用滴入 漏斗滴入與實施例1同法調製之異氰酸酯低聚物- 1與異 氰酸酯低聚物一 2之3 5 : 6 5重量份之苯溶液，於氮氣 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -29 - 583161 A7 B7 五、發明説明（27) C請先Μ讀背面之注意事項再填寫本I) 下攬拌之同時進行加熱迴流6小時。期間，藉由薄曆層析 法追踪反應之進行。反應結束後，減壓餾去溶媒後，取得 高粘度之無增殖性圖案低聚物（19g)。 〔實施例2〕 將1 · 2 g實施例1取得之鹼增殖性尿烷低聚物（1 )、0.2忌之3，4—環氧基環己甲基3，4—環氧基 環己烷羧酸鹼及0 . 02g之光鹼產生劑1，3 —雙（2 —硝基苄氧基羰基- 4 -吡啶基）丙烷溶於1 g之 THF後，作成試料。將此取得之試料溶液利用棒狀塗層 (No · 4)塗佈於76mmx26mm之玻璃基板後， 於1 1 0°C熱板上加熱1分鐘後，去除溶媒作成試料。針 對此塗膜其不同曝光時間下滑動光罩之同時使H g - X e 燈之紫外光未使用濾器進行照射後，更於1 1 0°C之熱板 上加熱1 5分鐘。此取得試料之表面以Η B鉛筆觀察其硬 化度結果示於表1。照射51分鐘後呈無粘性、照射 1 7 0分鐘後，於鉛筆硬度試驗中未出現傷痕。 經濟部智慧財產局員工消費合作社印製 〔比較例1〕 爲與具鹼增殖能之尿烷低聚物（1 )系之比較，針對 比較例1取得之未具鐘增殖能之尿烷低聚物系與實施例2 完全相同之操作下進行光硬化實驗。其評定結果示於表1 〇塗膜表面完全無粘度時所需光照射時間爲1 0 2分鐘， 證明導入鹼增殖裝置後，可提昇2倍試料之硬化效率。 本紙張尺度逋用中國國家標攀（CNS ) Α4规袼（210Χ297公釐） ^30.......- ~ 583161 A7 B7 五、發明説明（28) 表1 尿烷低聚物之硬化度 照射時間（min) 鹼增殖低聚物-A 圖案低聚物-B 0 X X 10 X X 34 Δ Δ 51 〇 △ 85 〇 Δ 136 〇 〇 170 ◎ 〇 — 1^------1 (請先聞讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 χ :與塗佈後相同。In the alkali-reactive composition, the proportion of the alkali-reactive substance is preferably 0.1 to 1 equivalent of the urethane residue in the alkali-proliferative prepolymer, and more preferably 0.4 to 5 equivalents, and more The best is 0.5 to 3 equivalents. A low-molecular alkali proliferative agent may be added to the alkali-reactive composition. As —7 i :: * Orders in j ^ (Please read the notes on the back before filling out this page) Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs The paper dimensions are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) -26-583161 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (24) For examples of low-molecular alkali proliferative agents, the aliphatic two represented by the general formula (4) can be used. A diurethane derivative obtained from an isocyanate and an alcohol represented by general formula (7). This diurethane derivative is proliferative to produce a primary amine. By adding this, the reaction of the alkali proliferative prepolymer can be further accelerated. Therefore, the reactivity of the resin composition can be improved. When necessary, supplementary ingredients such as pigments and silica particles can be added to the composition in an appropriate amount. The preferred alkali-reactive composition of the present invention is a polymer-reactive composition containing a polymerizable epoxide compound. This composition is polymerized by the action of light or heat, and then attached to a polymer. The preferred alkali-reactive composition of the present invention is one which starts a polymerization reaction by light. This composition is made of a polymerizable epoxy compound, an alkali-proliferative prepolymer, and a photobase generator, and may contain a low-molecular alkali proliferator, a polymerizable epoxy compound hardener, a hardening accelerator, and others if necessary. Composition of auxiliary ingredients such as tinctures. This composition can be effectively used as a pattern forming material and a film forming material. When forming a pattern using this photosensitive composition, for example, after dissolving the photosensitive composition in an organic solvent, a coating solution is prepared, and the coating solution is applied to an appropriate solid surface such as a substrate, and dried to form a coating. membrane. Alkali is generated after pattern exposure of this coating film. After further heat treatment, continuous decomposition of the alkali-producible prepolymer is promoted. The heat treatment conditions are changed according to the exposure energy, the type of the active alkali-proliferative prepolymer in the alkali used, the type of the epoxy compound, etc., and the general heating temperature is 60 ° C ~ 1 50 ° C, more preferably 80 ° C ~ 1 3 0 ° C. The heating time is from 10 seconds to 10 minutes, better,: --- ^-(Please read the precautions on the back before filling this page), and the paper size applies the Chinese National Standard (CNS) A4 specification ( 210X297 mm) _ 27-583161 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of invention (25) The time is 30 seconds to 5 minutes. This pattern was immersed in a solvent having a difference in solubility between the exposed and unexposed portions, and the pattern was obtained after development. When a film is formed from the photosensitive composition, for example, the photosensitive composition is dissolved in an organic solvent to form a coating solution, and the coating solution is applied to an appropriate solid surface such as a substrate and then dried to form a coating film. This coating film is irradiated with light to generate alkali. After further heat treatment, continuous decomposition of the alkali-proliferative prepolymer is promoted. The heat treatment conditions vary depending on its light energy, the type of active base proliferation prepolymer used, the type of epoxy compound, etc., and the general heating temperature is 60 ° C ~ 150 ° C, more preferably 80 ° C ~ 1 3 0 ° C. The heating time is 10 seconds to 10 minutes, and more preferably 30 seconds to 5 minutes. In this way, a hardened film of epoxy resin was formed on the solid surface. The solid surface includes glass, plastic, metal, ceramic, and the like. [Effects of the Invention] In the present invention, it is easy to cut off the urethane binding by the action of light and heat, and its multivalent primary amine produces a proliferative prepolymer at the end. Therefore, the composition formed by the compounds reacted with these The object is a thermal resin that senses heat and light. Such as: The coexistence of epoxy compounds can harden their composition by light and heat. The hardened product prepared in this way has a small volume shrinkage and good adhesion, and therefore, can harden the surface of the substrate. In addition, patterns can also be formed by exposing them in a pattern. Therefore, the composition of the present invention can be suitably applied to manufacturers of various ultraviolet curable inks, thermosetting paints, and the like.丨 丨 ^-^ ---- 丨 Loading ----: --- Order ------ Travel (Please read the precautions on the back before filling this page) This paper size applies to Chinese national standards (CNS ) A4 specification (210X297 mm) -28-583161 A7 B7 Printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (26) [Examples] The present invention will be described in detail by examples. [Example 1] (Synthesis of alkaline proliferative oligomer (1)) To 352 of dilauric acid di-n-butyltin (0.07, 0 · lmmo 1) was added 9- After dissolving the solution of fluorenylmethanol (4.5 g, 23mmo 1), it was heated and circulated under nitrogen to dissolve it. An isocyanate oligomer prepared by mixing 35 parts by weight of polytetramethylene glycol (molecular weight 20000) with 2 equivalents of isoflurone diisocyanate, 1, and 65 parts by weight of neopentyl glycol and A 15 g mixture of isocyanate oligomer-2 prepared from 2 equivalents of isoflurone diisocyanate was dissolved in 70 dehydrated benzene. This latter solution was dropped into the former solution through a dropping funnel, and then heated under reflux for 4 hours while stirring under nitrogen. During this period, the progress of the reaction was followed by thin layer chromatography. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a high-viscosity alkali-proliferative urethane oligomer (1) (20 g). [Comparative Example 1] (Synthesis of patterned oligomers without alkaline proliferation energy) 9-fluorenol (4.2g, 23mmo 1) was used instead of 9 in Example 1. Monomethyl alcohol was added to 3 5J. After lauric acid di-n-butyltin (0.07 g, 0.1 lmmo 1) was dehydrated in benzene, it was dissolved by heating under reflux under nitrogen. In this solution, an isocyanate oligomer-1 and an isocyanate oligomer 1-2 prepared in the same manner as in Example 1 were added dropwise using a dropping funnel to a 3 5: 6 5 parts by weight benzene solution under nitrogen (please read the back first) Please note this page before filling in this page) This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -29-583161 A7 B7 V. Description of invention (27) C Please read the notes on the back before filling in this I) Heat and reflux for 6 hours while stirring. During this period, the progress of the reaction was followed by thin-film chromatography. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a high-viscosity non-proliferative pattern oligomer (19 g). [Example 2] 1.2 g of the base-proliferative urethane oligomer (1) obtained in Example 1 and 0.2, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexyl An alkane carboxylic acid base and 0.02 g of a photobase generator 1,3-bis (2-nitrobenzyloxycarbonyl-4-pyridyl) propane were dissolved in 1 g of THF to prepare a sample. The obtained sample solution was coated on a glass substrate of 76 mm × 26 mm with a rod coating (No. 4), and heated on a hot plate at 110 ° C. for 1 minute, and then the solvent was removed to prepare a sample. After sliding the photomask under different exposure times on this coating film, the ultraviolet light of the H g-X e lamp was irradiated without a filter, and then heated on a hot plate at 110 ° C for 15 minutes. The surface of the obtained sample was observed in Table 1 with a 其 B pencil. There was no stickiness after 51 minutes of irradiation. After 170 minutes of irradiation, no scratches appeared in the pencil hardness test. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [Comparative Example 1] For comparison with the urethane oligomer (1) with alkaline proliferation energy, the urethane oligomer without bell proliferation energy obtained in Comparative Example 1 The material was subjected to a photohardening experiment under the same operation as in Example 2. The evaluation results are shown in Table 10. The light irradiation time required when the coating film surface is completely free of viscosity is 102 minutes, which proves that the introduction of the alkali multiplication device can increase the hardening efficiency of the sample by 2 times. This paper uses Chinese National Standards (CNS) A4 Regulation (210 × 297 mm) ^ 30 .......- ~ 583161 A7 B7 V. Description of Invention (28) Table 1 Hardening of urethane oligomers Degree irradiation time (min) Alkali proliferation oligomer-A Pattern oligomer-B 0 XX 10 XX 34 Δ Δ 51 〇 △ 85 〇Δ 136 〇〇170 ◎ 〇— 1 ^ ------ 1 (Please First read the notes on the back and then fill out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs χ: Same as after coating.
I △:稍有硬化，惟，碰觸後仍粘腻。 訂 〇：以鉛筆畫過出現刮痕、惟，碰觸時不會粘粘。 丨.I △: Slightly hardened, but still sticky after touching. Order 〇: Scratches, but scratches, but not sticky when drawn with a pencil.丨.
◎:以鉛筆畫亦無刮痕，碰觸亦不會粘粘。 I 〔實施例3〕 ^◎: No scratches when drawing with a pencil, and no stickiness when touching. I [Example 3] ^
將1 . 2 g之實施例1取得鹼增殖低聚物（1 ) 、 I 0 · 5g之由六亞乙基二異氰酸酯與9 -芴基甲醇所取得 | 之鹼增殖劑、0 . 4g之三羥甲基丙烷三縮水甘油醚以及 11.2 g of Example 1 was obtained as an alkali-proliferation oligomer (1), and I 0.5 g was obtained from a hexaethylene diisocyanate and 9-fluorenyl methanol. Methylolpropane triglycidyl ether and 1
0 . 02g之光鹼產生劑之1 ，3 -雙（2 —硝基苄氧基 -I0.02g of 1,3-bis (2-nitrobenzyloxy-I
羰基-4 一吡啶基）丙烷溶於1 g之T H F後作成試料。 I 將此取得試料溶液與實施例1同法塗佈於玻璃基板上，於 | 1 10 °C熱板上加熱1分鐘後去除溶媒，進行照射由Hg 一 X e燈之光後，於1 1 0 °C下進行加熱。1 5分鐘之照 | | 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -31 - ' 583161 A7 _B7_五、發明説明（29) 射下觀察HB硬化度。 〔實施例4〕 將1 · 2 g實施例1取得之鹼增殖低聚物（1 )、 0 . 5g由9 一芴基甲醇與六亞甲基二異氰酸酯所取得之 鹼增殖劑、0 . 6g之三羥甲基丙烷三縮水甘油醚以及0 • 0 2g之光鹼產生劑之1 ，3 —雙（2 -硝基苄氧基鑛 基一 4 一吡啶基）丙烷溶於lg之T：HF中，作成試料。 將此取得之試料溶液與實施例1同法塗佈於玻璃基板後， 於1 1 0 °C熱板上加熱1分鐘後去除溶媒，照射由 Hg - Xe燈之光後，於1 1 〇°C下進行加熱。1 〇分鐘 照射中觀察其Η B硬化度。 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 〔實施例5〕 將伸乙基偕醇腈（1 . 6 3 g，2 3 m m ο 1 )溶於 35m£ 含二月桂酸二—正—丁錫（〇 · 〇7g，〇 . 1 mmo 1 )之脫水苯中。再將3 5重量份聚四亞甲基二醇 (分子量2 0 0 0 )與2當量異氟爾酮二異氰酸酯所調成 之異氰酸酯低聚物1與6 5重量份之新戊二醇與2當量異 氟爾酮二異氰酸酯所調製而成之異氰酸酯低聚物2所成之 1 5 g混合物溶於7 〇 4脫水苯。利用滴入漏斗將該後者 溶液滴入前者溶液後，於氮氣下進行攪拌同時加熱迴流4 小時。期間藉由薄層層析法進行追踪反應之進行。反應結 束後，減壓餾去溶媒後，取得鹼增殖尿烷低聚物（2 )。 本紙張尺度適用中國國家標準（CNS ) Α4規格（21〇χ297公釐）· 32 _ 583161 A7 Β7 五、發明説明（30) 將1 · 0g此低聚物、〇 · 6g之三羥甲基丙烷三縮水甘 油醚及0 · 02g光鹼產生劑之1 ，3 —雙（2 -硝基苄 氧基羰基一4一吡啶基）丙烷溶於1g THF後作成試 料。將該取得試料溶液與實施例1同法塗佈於玻璃基板後 ，於1 1 0 °C熱板上加熱1分鐘後去除溶媒之後，照射Η g - X e燈之光後，於1 1 〇 °c下進行加熱。1 〇分鐘照 射中觀察其Η B硬化度。 (請先閱讀背面之注意事項再填寫本頁) 、τ 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐） -33 -Carbonyl-4 -pyridyl) propane was dissolved in 1 g of T H F to prepare a sample. I The obtained sample solution was coated on a glass substrate in the same manner as in Example 1. After heating on a hot plate at 10 ° C for 1 minute, the solvent was removed, and the light was irradiated by the light of Hg-Xe lamp at 1 1 Heat at 0 ° C. 1 5-minute photo | | This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) -31-'583161 A7 _B7_ V. Description of the invention (29) Observe the HB hardening degree by shooting. [Example 4] 1.2 g of the base multiplying oligomer (1) obtained in Example 1, 0.5 g of the base multiplying agent obtained from 9-methanol and hexamethylene diisocyanate, 0.6 g Trimethylolpropane triglycidyl ether and 0 • 0 2g of photobase generating agent 1,3-bis (2-nitrobenzyloxymine 4-4-pyridyl) propane dissolved in lg of T: HF In the test sample. After applying the obtained sample solution to a glass substrate in the same manner as in Example 1, heating it on a hot plate at 110 ° C for 1 minute, removing the solvent, and irradiating the light from a Hg-Xe lamp at 1 110 ° Heated at C. The degree of ΗB hardening was observed during 10 minutes of irradiation. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs [Example 5] Dissolve ethylenol (1.63 g, 2 3 mm ο 1) in 35m £ Dehydrated benzene containing di-n-butyltin dilaurate (0.07 g, 0.1 mmo 1). Then, 35 parts by weight of polytetramethylene glycol (molecular weight 20000) and 2 equivalents of isoflurane diisocyanate are prepared from isocyanate oligomers 1 and 65, and 5 parts by weight of neopentyl glycol and 2 A 15 g mixture of an isocyanate oligomer 2 prepared from an equivalent of isoflurone diisocyanate was dissolved in 70% dehydrated benzene. This latter solution was dropped into the former solution using a dropping funnel, and then heated under reflux for 4 hours while stirring under nitrogen. During this period, the reaction was followed by thin layer chromatography. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain an alkali-proliferated urethane oligomer (2). This paper size applies Chinese National Standard (CNS) A4 specification (21 × 297 mm) · 32 _ 583161 A7 B7 V. Description of the invention (30) 1.0 g of this oligomer and 0.6 g of trimethylolpropane Triglycidyl ether and 0.02 g of 1,3-bis (2-nitrobenzyloxycarbonyl-4-pyridyl) propane were dissolved in 1 g of THF to prepare a sample. The obtained sample solution was applied to a glass substrate in the same manner as in Example 1. After heating on a hot plate at 110 ° C for 1 minute, the solvent was removed, and then the light of a g-Xe lamp was irradiated. ° C. The degree of ΗB hardening was observed during 10 minutes of irradiation. (Please read the precautions on the back before filling this page), τ Printed by the Consumer Cooperatives of Intellectual Property Bureau of the Ministry of Economic Affairs This paper size applies to China National Standard (CNS) Α4 specification (210 X 297 mm) -33-
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000324487A JP2002128750A (en) | 2000-10-24 | 2000-10-24 | Base proliferating prepolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW583161B true TW583161B (en) | 2004-04-11 |
Family
ID=18802009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW90126301A TW583161B (en) | 2000-10-24 | 2001-10-24 | Base-proliferation prepolymers |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2002128750A (en) |
| TW (1) | TW583161B (en) |
| WO (1) | WO2002034714A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005060520A (en) * | 2003-08-12 | 2005-03-10 | Konica Minolta Medical & Graphic Inc | Curable composition, ink for inkjet using the same, and method of forming cured product |
| JP4570413B2 (en) * | 2004-07-26 | 2010-10-27 | 旭化成イーマテリアルズ株式会社 | Photoreactive compound and photocurable composition using the same |
| JP3884758B2 (en) | 2005-03-11 | 2007-02-21 | 積水化学工業株式会社 | Base proliferating agent and base-reactive curable composition |
| US8236476B2 (en) | 2008-01-08 | 2012-08-07 | International Business Machines Corporation | Multiple exposure photolithography methods and photoresist compositions |
| JP5516195B2 (en) | 2009-08-04 | 2014-06-11 | 信越化学工業株式会社 | Pattern forming method and resist material |
| JP6132554B2 (en) * | 2013-01-08 | 2017-05-24 | アイバイツ株式会社 | Photobase generator composition |
| WO2014185303A1 (en) * | 2013-05-13 | 2014-11-20 | 和光純薬工業株式会社 | Thioxanthene compound, base amplifier, and base-reactive resin composition containing base amplifier |
| JP6156875B2 (en) * | 2013-08-27 | 2017-07-05 | 学校法人東京理科大学 | Base proliferating agent and base-reactive resin composition containing the base proliferating agent |
| TWI781295B (en) | 2018-02-26 | 2022-10-21 | 日商日本化藥股份有限公司 | Base proliferating agent and base reactive resin composition containing the base proliferating agent |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5930919A (en) * | 1982-08-16 | 1984-02-18 | Toray Ind Inc | Water repellency, oil repellency, and antifouling treatment of synthetic yarn |
| JP2660507B2 (en) * | 1985-05-31 | 1997-10-08 | 大日本インキ化学工業株式会社 | Coating agent |
| JP3847452B2 (en) * | 1998-05-07 | 2006-11-22 | 富士写真フイルム株式会社 | Photosensitive planographic printing plate |
| EP1225478B1 (en) * | 1998-04-06 | 2012-12-19 | FUJIFILM Corporation | Photosensitive resin composition |
-
2000
- 2000-10-24 JP JP2000324487A patent/JP2002128750A/en active Pending
-
2001
- 2001-10-24 WO PCT/JP2001/009343 patent/WO2002034714A1/en active Application Filing
- 2001-10-24 TW TW90126301A patent/TW583161B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| WO2002034714A1 (en) | 2002-05-02 |
| JP2002128750A (en) | 2002-05-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI225183B (en) | A diaryliodonium salt of the formula I, a radiation-sensitive composition comprising the diaryliodonium salt and uses of the compositions and the diaryliodonium salt | |
| TW583161B (en) | Base-proliferation prepolymers | |
| JP5516574B2 (en) | Base generator, photosensitive resin composition, pattern forming material comprising the photosensitive resin composition, pattern forming method and article using the photosensitive resin composition | |
| JP5561693B2 (en) | Novel compound, base generator and photosensitive resin composition containing the base generator | |
| US20130012611A1 (en) | Synergists | |
| JP6011956B2 (en) | Photosensitive resin composition | |
| JP5712926B2 (en) | Base generator, photosensitive resin composition, pattern forming material comprising the photosensitive resin composition, pattern forming method and article using the photosensitive resin composition | |
| JP2002265531A (en) | Base-proliferating unsaturated compound, base- proliferating resin, and composition containing the resin | |
| WO2006095670A1 (en) | Base multiplying agents and base-reactive curable compositions | |
| CN108368036A (en) | Compounds containing Photoepolymerizationinitiater initiater made of the compound and contain the photosensitive polymer combination of the Photoepolymerizationinitiater initiater | |
| Shirai | Photocrosslinkable polymers with degradable properties | |
| TWI742178B (en) | Thin film material and pattern forming method | |
| JPWO2014155960A1 (en) | Photobase generator | |
| JP5446793B2 (en) | Photosensitive resin composition, article using the same, and negative pattern forming method | |
| TWI241459B (en) | Positive photosensitive resin composition, positive photosensitive dry film and method of forming pattern | |
| Min et al. | UV-curable nanoimprint resist with liquid volume-expanding monomers | |
| Shirai et al. | UV‐curable positive photoresists for screen printing plate | |
| JP5224016B2 (en) | Active energy ray base generator, active energy ray base generator composition, base-reactive composition, and pattern forming method | |
| Perrot et al. | UV‐curable thio‐ether‐urethane network with tunable properties | |
| WO2004017141A1 (en) | Optical image recording material, hologram base body, method of optical image recording and process for producing optical image recording material and hologram base body | |
| CA1126436A (en) | Photopolymerizable composition containing an acid-polymerizable material, an iodonium salt and a free radical generator | |
| JP2010222586A (en) | Base generator and photosensitive resin composition comprising the same | |
| JP5515560B2 (en) | Photosensitive resin composition, pattern forming material comprising the photosensitive resin composition, pattern forming method, article using the photosensitive resin composition, and photolatent resin curing accelerator | |
| JP2012113256A (en) | Photosensitive resin composition | |
| TW419615B (en) | Photo crosslinkable, aqueous base developable negative photoresist composition and method for use thereof |