TW392092B

TW392092B - Oximesulfonic acid esters and the use thereof as latent sulfonic acids

Info

Publication number: TW392092B
Application number: TW85112555A
Authority: TW
Inventors: Kurt Dietliker; Martin Kunz
Original assignee: Ciba Sc Holding Ag
Priority date: 1996-10-15
Filing date: 1996-10-15
Publication date: 2000-06-01

Description

A7 B7A7 B7

·-·丨 π 一一· ·修正I 經濟部中央標準局員工消費合作社印製五、發明説明（) 被倒入水中且Μ亞甲基氛進行萃取數次。於硫酸鎂上進行乾燥後，將溶劑為於一旋轉性揮發器中蒸餾去除。剰下的的棕色油狀物隨後經由快速色層分析於矽膠（洗提劑：石油醚/乙酸乙酯 3: 1)上進行純化。14.75公克（41% )之α — （4 一十二烷基苯基磺醢基氧亞胺基）—3，4一二甲氧基苄基氰化物以黏稠狀黃色油狀物的形式得到。1 Η_ NMR光譜顯示其為順式（syn)異構物°UV/Vis光譜（乙腈 )顯示在350微毫米（e =10700)，其延伸至435微毫米，有一吸收帶。·-· 丨 π -11 · · Revision I Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention () Poured into water and extracted with methylene methane several times. After drying over magnesium sulfate, the solvent was distilled off in a rotary volatilizer. The brown oil that was left over was then purified by flash chromatography on silica gel (eluent: petroleum ether / ethyl acetate 3: 1). 14.75 g (41%) of α- (4-dodecylphenylsulfonyloxyimino) -3,4-dimethoxybenzyl cyanide was obtained as a viscous yellow oil. 1 Η NMR spectrum shows that it is a cis (syn) isomer. UV / Vis spectrum (acetonitrile) shows at 350 micrometers (e = 10700), which extends to 435 micrometers, and has an absorption band.

兀素分析： C2 8 H3 8尺2 〇5 S c C % ] Η [ % ] Ν [ % 3 S 〔％〕計算值： 65.34 7.44 5.44 6.23 發現值： 64.87 7.36 5.49 6.14 實施例5 : 〇t - （ 2—丙基磺醯基氧亞胺基）二甲氧基苄基氰化物如1.2所述， 16.5公克（0.08莫耳）之α -羥基亞胺基_3，4 —二甲氧基苄基氰化物與12.6公克（0·088冥耳）之 2—丙烷磺醢基氯化物在三乙基胺的存在下進行反懕。粗製產物自乙酸乙酯/己烷進行再结晶得到 2 1 · 9公 -68* 本紙張尺度適用中國國家榇华（CNS ) A4g格（210Χ2Ή公釐） ^1.^1 In -1-!*= I- -1« nn ml m· InTJ 03 言 (請先閱讀背面之注意事項再填寫本頁) 經濟部中夬標準局員工消費合作社印製 A7 _· B7__ 五、發明説明（j ) 本發明相閫於可光聚合性組成物類，其包括肟磺酸酯類，並相Μ於化合物作為長波長一可活化的沉潛性磺酸光起動劑類。 ΕΡ-Α- 139609揭示表面一被覆組成物類，其基於感光性肟磺酸酯類及慣用的酸-可熟化的樹脂類。 ΕΡ- A 5 7 1 3 3 0揭示α -( 4-甲苯-磺醢基氧亞胺基 )一 4一甲氧基苄基氰化物及α — （4 —甲苯一磺醢基氧亞胺基）-3 -睡嗯基甲基氰化物作為正性及負性光Ρ且物質類針對波長34Q— 3 9 0微笔米之沉潛性酸提供者，特別是那些在水銀i頻帶（ 36 5微毫米）之輻射區域的波長。在本技藝中對反應性非離子性沉潛性酸提供者仍存在一種需要•特別是當以長波長光進行輻射時，該反應性非離子性沉潛性酸提供者為熱及化學上安定的且，在被光活化之後，可作為觸媒類K供多樣性酸-催化性反應*如聚縮合反應，酸-催化性解聚作用反應，酸-催化性親核性取代反應或酸一催化性之保護性基團去除。對於能Μ光進行辐射時可轉化成酸類且為能夠在組抗物配方中作為溶解性抑制劑類的化合物類。，亦有此需要令人驚異地，現已發現特異性肟磺酸酯類為特別合適 -5- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ---------l·裝------訂------镍 (請先閲讀背面之注意事項再填寫本頁)Element analysis: C2 8 H3 8 feet 2 〇5 S c C%] Η [%] Ν [% 3 S 〔%] Calculated value: 65.34 7.44 5.44 6.23 Found value: 64.87 7.36 5.49 6.14 Example 5: 〇 t- (2-propylsulfonyloxyimino) Dimethoxybenzyl cyanide As described in 1.2, 16.5 g (0.08 mole) of α-hydroxyimido-3,4-dimethoxybenzyl The cyanide was reacted with 12.6 g (0.088 gram) of 2-propanesulfonyl chloride in the presence of triethylamine. The crude product was recrystallized from ethyl acetate / hexane to obtain 2 1 · 9 Kg-68 * This paper size applies to China National Hua (CNS) A4g grid (210 × 2Ήmm) ^ 1. ^ 1 In -1-! * = I- -1 «nn ml m · InTJ 03 (please read the precautions on the back before filling this page) Printed by A7 _ · B7__ of the Consumer Cooperatives of the China Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (j) The invention It is related to photopolymerizable compositions, which include oxime sulfonates, and is related to compounds as long-wavelength, activatable, latent sulfonic acid photostarters. EP-A-139609 discloses a surface-coating composition based on a photosensitive oxime sulfonate and a conventional acid-curable resin. Ep-A 5 7 1 3 3 0 reveals α- (4-toluene-sulfonyloxyimino) -4-methoxybenzyl cyanide and α- (4-toluene-sulfonyloxyimino) ) -3-Sylmethyl cyanide as a positive and negative light P and the substance class is a latent acid provider with a wavelength of 34Q-3 0 0 micrometers, especially those in the mercury i band (36 5 micrometers) Millimeter). There is still a need for reactive nonionic latent acid providers in the art. Especially when irradiated with long wavelength light, the reactive nonionic latent acid provider is thermally and chemically stable and After being activated by light, it can be used as a catalyst K for a variety of acid-catalytic reactions such as polycondensation reactions, acid-catalytic depolymerization reactions, acid-catalytic nucleophilic substitution reactions or acid-catalytic reactions. The protective group is removed. Compounds that can be converted into acids when irradiated with M light are compounds that can be used as solubility inhibitors in the formulation of antibodies. There is also a need for this surprisingly. It has been found that specific oxime sulfonates are particularly suitable. -5- This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) ------- --l · install ------ order ------ nickel (please read the precautions on the back before filling this page)

A7 BT 五、發明説明（·)/) 作為此類反懕的觸媒本發明據此相關於一種可光活化的組成物，其包括 a)至少一種化合物，其可於酸的作用下被交叉瞄结及 /或 b)至少一種化合物，其溶解度在酸的作用下被改變及 c)作為光起動劑之至少一種式I之化合物A7 BT 5. Description of the invention (·) /) As a catalyst for this kind of reaction, the present invention is accordingly related to a photoactivatable composition including a) at least one compound which can be cross-linked under the action of an acid Target and / or b) at least one compound whose solubility is altered by the action of an acid and c) at least one compound of formula I as a light starter

Rr 0 II -C- C=N-〇-S〇i I 2 «2 ---------丨装------IT------@ (請先閩讀背面之注意事項再填寫本頁) ®-^郎中夬樣隼局員工消費合作狂印装其中π為0或1且X為1或2 ;Rr 0 II -C- C = N-〇-S〇i I 2 «2 --------- 丨 Installation ------ IT ------ @ (Please read the back first (Please note this page before filling in this page) ®- ^ Langzhong 夬 Sample Bureau employee consumer cooperation printing, where π is 0 or 1 and X is 1 or 2;

Ri為苯基，其經由一種或多種自由基加以取代，該自由基可為Cl — Cl 2综基，Ci —C4齒焼基，苯基’ 〇丘4 ，SR4及/或NRs Rs ;取代基〇R4 ，SR4及NRs Re有可能形成5-或6-員環，該環的形成係藉由自由基IU ，Rs 本紙張尺度適用中國國家揉準（CNS ) A4规格（210X297公釐）經濟部中央標率局員工消费合作社印製 A7 B7 五、發明説明（j ) 及/或Re ，環上具有進一步的取代基或具有苯環上碳原子之一，其條件為當該苯環經由甲氧基進行取代時*在該環上至少出現一個進一步之取代基，或為萘基，憩基或菲基；自由基萘基，趙基及菲基為未經取代的或經由-C 6烷基，苯基，OR4 ，SR4及/或經由NRS Rs加K取代，取代基OR4 ，SR4及NRS Re有可能形成5—或6-員環，該環的形成係經由自由基R4 ，R5及/SR6 ，環上具有進一步的取代基或具有萘基，憩基或菲基環上碳原子之一，或R 1為一雜芳基自由基，其為未經取代的或經由Ci _CS烷基，苯基，0R4 ，SR4及/或經由NRS R6加以取代，取代基0R4 ，SR4及NR5 Rs有可能形成5—或6—員環，該環的形成係藉由自由基R4 ，Rs及/或Rs ，環上具有進一步的取代基或具有雜芳基環上碳原子之一，其條件為Ri不為未經取代的噻嗯基； R2具有定義之一或為未經取代的或CN—取代之苯基，C2_C6 —垸睡基，苄醢基，其為未經取代的或經由 Ci —C6院基，苯基，OR4 ， SR4及/或經由NRs Re加 K取代，C2 — C6烷氧基羰基，苯氧基羰基，R5 R6 N，嗎啉基，呢啶基，dCi-C*鹵烷基，StiHnCi-C 6焼基，未經取代的或Ci 一 Ci 2院基一取代的 S(〇) η —Cs — Ci 2 芳基，SO2 〇—Ci — Ce 院基， S〇2 0— Cs 一 Ci 〇芳基或NHCONH2 ，其中n為1或2; -7 * 本紙張尺度適用中國國家標準（CNS ) Μ規格（210X29?公釐） ----------裝------IT------0 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消费合作社印製 A7 1 B7 五、發明説明（f) 或R i及 Rz ，若合適時則共同與C0基圑，形成一 5 一或6—員環，其為未經取代的或經由 Ci _C6烷基，苯基， OIU ， SR4或經由NRs IU加Μ取代且其可額外地被 0， S， NRs及/或被C0加Κ中斷且一種或多種苯並自由基可與其稠合；Ri is phenyl, which is substituted via one or more free radicals, which may be Cl—Cl 2 heptyl, Ci—C 4 dentyl, phenyl ′ 〇丘 4, SR4 and / or NRs Rs; substituents 〇R4, SR4 and NRs Re may form a 5- or 6-membered ring. The ring is formed by free radicals IU, Rs. This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) Ministry of Economic Affairs Printed by A7 B7 of the Consumer Standards Cooperative of the Central Bureau of Standards. 5. Description of the invention (j) and / or Re, with further substituents on the ring or one of the carbon atoms on the benzene ring, provided that the benzene ring passes through methoxy When substituents are substituted * at least one further substituent appears on the ring, or is a naphthyl, aloyl, or phenanthryl; the radical naphthyl, zhao, and phenanthryl are unsubstituted or via -C 6 alkyl , Phenyl, OR4, SR4 and / or substituted by NRS Rs plus K, the substituents OR4, SR4 and NRS Re may form a 5- or 6-membered ring, the formation of this ring via the radicals R4, R5 and / SR6 , Has a further substituent on the ring or has one of the carbon atoms on the naphthyl, aryl or phenanthryl ring, or R 1 is a heteroaryl Free radicals, which are unsubstituted or substituted via Ci_CS alkyl, phenyl, OR4, SR4 and / or NRS R6, the substituents OR4, SR4 and NR5 Rs may form a 5- or 6-membered ring, The ring is formed by radicals R4, Rs and / or Rs, with further substituents on the ring or with one of the carbon atoms on the heteroaryl ring, provided that Ri is not an unsubstituted thienyl; R2 has one of the definitions or is unsubstituted or CN-substituted phenyl, C2_C6—suldinyl, benzamidine, which is unsubstituted or via Ci—C6 alkyl, phenyl, OR4, SR4 and / Or substituted by K through NRs Re, C2-C6 alkoxycarbonyl, phenoxycarbonyl, R5 R6 N, morpholinyl, morpholinyl, dCi-C * haloalkyl, StiHnCi-C 6 fluorenyl, unsubstituted Substituted or Ci-Ci 2 courtyard-substituted S (〇) η —Cs — Ci 2 aryl, SO 2 0 —Ci — Ce courtyard, S 2 0 — Cs — Ci 0 aryl or NHCONH 2, where n is 1 or 2; -7 * This paper size is applicable to China National Standard (CNS) M specifications (210X29? mm) ---------- installation ------ IT ----- -0 (Please read the notes on the back before filling (This page) Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 1 B7 V. Description of invention (f) or R i and Rz, if appropriate, together with C0 basis to form a 5 1 or 6-member ring Is unsubstituted or substituted via Ci_C6 alkyl, phenyl, OIU, SR4 or via NRs IU plus M and it may be additionally interrupted by 0, S, NRs and / or C0 plus K and one or more benzo Free radicals can be fused with it;

R3 ，當 X為1時，為Ci-Cis烷基，苯基一Ci-C 3烷基，揮腦基，Ci-Cio鹵烷基，苯基，萘基，憩基或菲基；自由基苯基，萘基，爵基及菲基為未經取代的或經由一種或多種自由基鹵素， Ci — C4鹵烷基，CN， N0 2 ， Ci-Cis 烷基* 苯基，〇R4 ， C00R7 * - 0C0- C 1 — C4焼基' S〇2 OR7及/或經由Rs Re N加Μ取代，或 R3 ，當X為2時，為C2— Cl2亞烷基，亞苯基，亞萘基，，二亞苯基或氧二亞苯基，自由基亞苯基，亞萘基，，二亞苯基及氧二亞苯基為未經取代的或經由Ci — Ci 2 烷基加以取代； R4為氫，一（^ Z烷基，其為未經取代的或經由 -8- 本紙張尺度適用中國國家標準（CNS )八4«1格（210X297公釐） ---------l·裝------訂·------線 (請先《讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 A7 'B7 五、發明説明（f) 苯基， OH* Ci -Ci 2烷氧基，Ci -C! 2烷基磺醢基，苯基磺醢基，（4_甲基苯基）磺醢基及/或經由C2 — Cs烷醢基加以取代且其額外地被- 0 -中斷，或為苯基；R3, when X is 1, Ci-Cis alkyl group, phenyl-Ci-C 3 alkyl group, Cinnayl group, Ci-Cio haloalkyl group, phenyl group, naphthyl group, alkyl group or phenanthryl group; radical Phenyl, naphthyl, methyl and phenanthryl are unsubstituted or via one or more free radical halogens, Ci — C4 haloalkyl, CN, NO 2, Ci-Cis alkyl * phenyl, OR4, C00R7 *-0C0-C 1-C4 fluorenyl 'S〇2 OR7 and / or substituted by Rs Re N plus M, or R3, when X is 2, it is C2-Cl2 alkylene, phenylene, naphthylene ,, Diphenylene or oxydiphenylene, radical phenylene, naphthylene,, diphenylene and oxydiphenylene are unsubstituted or substituted by Ci—Ci 2 alkyl; R4 is hydrogen, a (^ Z alkyl, which is unsubstituted or via -8- This paper size applies Chinese National Standard (CNS) 8 4 «1 grid (210X297 mm) -------- -l · Assembly ------ Order · ------ line (please read "Notes on the back before filling this page") Printed by A7 'B7, Shellfish Consumer Cooperative, Central Standards Bureau, Ministry of Economic Affairs V. Invention Explanation (f) phenyl, OH * Ci -Ci 2 alkoxy, Ci -C! 2 alkylsulfonyl, phenyl Minced meat group, (4_ methylphenyl) sulfo group and minced meat / or via a C2 - Cs alkyl radical addition to a substituted Dukes and which is additionally - 0 - interrupt, or phenyl;

Rs及R6彼此獨立為氫或Ci —Ci 2烷基，其為未經取代的或經由0H，（^一（：4烷氧基，Ci -Ci 2烷基磺醢基，苯基磺醢基，（4 一甲基苯基）-磺醢基及/或經由 Ci — C6烷醢基加Μ取代且其可額外地被一 0—所中斷，或 Rs及Re為苯基，C2 — C6烷醢基*苄睡基，Ci _CS 烷基磺醢基，苯基磺醢基，（4一甲基苯基）磺醸基，萘基磺醢基，憩基磺醢基或菲基磺醢基，或Rs及Rs ，共同與他們所連结的氮原子，形成一 5_， 6-或7 -員環，其可由_〇 —或由一 NR4 —加以中斷；且R7為-Ci 2烷基，其為未經取代的或經由 0H 及/或由 Cl — C4烷氧基加以取代，且其可額外地被一 0 —加以中斷。Rs and R6 are each independently hydrogen or Ci-Ci 2 alkyl, which is unsubstituted or via 0H, (^-(4 alkoxy, Ci-Ci 2 alkylsulfonyl, phenylsulfonyl) , (4-methylphenyl) -sulfonyl and / or substituted via Ci-C6 alkylfluorenyl plus M and it may be additionally interrupted by a 0-, or Rs and Re are phenyl, C2-C6 alkyl Fluorenyl * benzyl, Ci_CS alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl, naphthylsulfonyl, sulfosulfanyl or phenanthrenesulfonyl , Or Rs and Rs, together with the nitrogen atom to which they are attached, form a 5_, 6- or 7-membered ring, which can be interrupted by _0-or -NR4-; and R7 is -Ci 2 alkyl, It is unsubstituted or substituted via 0H and / or by a Cl—C4 alkoxy group, and it can be additionally interrupted by a 0—.

Ci -Ci 8烷基為直鐽狀或分枝狀且為，例如， Ci —c 1 z ~， C I — C 8 —， C 1 — C 6 —或 Cl — C 4 —院基。實施例為甲基，乙基，丙基，異丙基， η—丁基，第二一丁基，異丁基，第三一丁基，戊基，己基，庚基，2，4 ，4 —三甲基戊基，2 —乙基己基，辛基，壬基，癸基， -9- 本紙張尺度適用中國國家揉準（〇阳）八4^格（210/297公釐） --------—裝------1Τ------.^ (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局負工消费合作社印装 A7 • B7 五、發明説明（& ) 十一烷基，十二烷基，十四烷基，十五烷基，十六烷基，十t烷基及十八烷基。例如，R3為（^ _Ca烷基，特別是（；1一（：6烷基，偏好為（：1_{：4烷基，如甲基，異丙基或丁基。Ci -Ci 8 alkyl is straight or branched and is, for example, Ci —c 1 z ~, C I — C 8 —, C 1 — C 6 — or Cl — C 4 — courtyard. Examples are methyl, ethyl, propyl, isopropyl, η-butyl, second monobutyl, isobutyl, third monobutyl, pentyl, hexyl, heptyl, 2, 4, 4 —Trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, -9- This paper size applies to Chinese national standard (0 Yang) 8 4 ^ grid (210/297 mm)- ------— Installation ----- 1T ------. ^ (Please read the precautions on the back before filling out this page) Printed by A7 • B7, Consumers Cooperatives, Central Bureau of Standards 5. Description of the invention (&) Undecyl, dodecyl, tetradecyl, pentadecyl, cetyl, decyl and octadecyl. For example, R3 is (^ _Ca alkyl, especially (; 1-(: 6 alkyl), preference is (: 1_ {: 4 alkyl, such as methyl, isopropyl or butyl.

Ci -Ci s烷基及Ct - G 2烷基為同樣為直鐽狀或分枝狀且為，例如，如上所.定義達到合適數目的碳原子。有利者為，例如，C i 一 c8 —，特別是c 1 一“一，偏好為Ci -c4 一烷基，如甲基或丁基。Ci-Ci s alkyl and Ct-G 2 alkyl are also straight or branched and are, for example, as defined above, to the appropriate number of carbon atoms. Advantages are, for example, Ci-c8 —, especially c 1-"one, and preference is Ci-c4-alkyl, such as methyl or butyl.

被一 0 一或一 S -中斷一次或數次的C2 -Ci 2烷基，例如，被一〇一中斷，一至五次，例如自一至三次或一次或兩次。這些结果在结構單元如：一 S ( CH2 ) 2 0H , 一〇 ( CH2 ) 2 OH * - 〇 ( CHz ) 2 〇CH3 * - 〇 ( CHz CHz 0) 2 CHz CH3 - - CH2 - 〇- CHs > - CH2 CH2 - CHz CH3 ,-〔ch2 CH2 〇] y- CHs ，其中 y= 5 ’ _ ( CHz CH2 0) s CH2 CH3 , - CH2 _ CH ( CH3 ) _ 0_ CH2 - CHz CH 3 或-CHz - CH ( CH3 ) - o- CH2 - CH3 ° c5 - Ci 2環烷基為，例如，環戊基，環己基’環辛基，環十二烷基，特別是環戊基及環己基，偏好為環己基 -10- 本紙張尺度速用中國國家揉準（CNS)A4規格（210x297公釐）裝------訂------镍 (請先閲讀背面之注意事項再填寫本頁) .經濟郎中央慄隼局員Η消費合作社印裂 A7 * B7 五、發明説明（7 ) C2 2亞烷基為直鍵狀或分枝狀且為，例如，C2 — 8 -，C2 - Cs -或C2-C4 -亞烷基。實施例為亞乙基，亞丙基*亞丁基，亞戊基，亞己基，亞庚基，亞辛基，亞壬基，亞癸基，亞十一烷基及亞十二烷基。例如，r3為{：1 —C8亞烷基，特別是（^ — C6亞烷基•偏好為（^ — C4亞烷基，如亞甲基或亞丁基。經取代的苯基擁帶自一個至五個，例如一，二或三個，特別是一個或兩個在苯環上的取代基。該取代偏好在苯環之 4一，3，4一，3，5 —或 3，4，5— 位置。當自由基萘基 > 菲基，雜芳基及爵基為經由一個或多個自由基加以取代時，他們為，例如，單——至伍一經取代的，例如單——，二一或三一經取代的，特別是簞—— 或二一經取代的。當I為一經取代的苯基自由基，其經由OR4 * SR4及 /或經由NR5 Rs加Μ取代且取代基01U ，SR4及髓5 Re 形成5_或6—員環時，該環的形成係藉由自由基IU ，Rs 或1^ ，環上具有其他的取代基或具有苯環碳原子之，例如可得到下列的结構 -11- 本紙张尺度適用中國國家標準（CNS)A4規格（2丨0X297公釐） --------—r------IT------φ (請先閲讀背面之注意事項再填寫本頁) A7 五、發明説明（(f )A C2-Ci 2 alkyl group interrupted one or several times by one or one S-, for example, interrupted by one one, one to five times, such as one to three or one or two times. These results are in structural units such as: -S (CH2) 2 0H, -〇 (CH2) 2 OH *-〇 (CHz) 2 〇CH3 *-〇 (CHz CHz 0) 2 CHz CH3--CH2-〇-CHs >-CH2 CH2-CHz CH3,-[ch2 CH2 〇] y- CHs, where y = 5 '_ (CHz CH2 0) s CH2 CH3,-CH2 _ CH (CH3) _ 0_ CH2-CHz CH 3 or -CHz -CH (CH3)-o- CH2-CH3 ° c5-Ci 2 cycloalkyl is, for example, cyclopentyl, cyclohexyl 'cyclooctyl, cyclododecyl, especially cyclopentyl and cyclohexyl, preference For cyclohexyl-10- This paper size is quickly used in China National Standard (CNS) A4 (210x297 mm) Packing --- Order --- Nickel (Please read the notes on the back before filling (In this page) .Economy Central Lishui Bureau member ΗConsumer Cooperative Printing A7 * B7 V. Description of the invention (7) C2 2 alkylene is straight or branched and is, for example, C2 — 8-, C2- Cs-or C2-C4-alkylene. Examples are ethylene, propylene * butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylidene, and dodecylidene. For example, r3 is {: 1 —C8 alkylene, especially (^ — C6 alkylene • preference is (^ — C4 alkylene, such as methylene or butylene. The substituted phenyl group carries one To five, such as one, two, or three, especially one or two substituents on the benzene ring. The substitution preference is 4 to 1, 3, 4 one, 3, 5 — or 3, 4, 5-position. When the free radical naphthyl > phenanthryl, heteroaryl and phenyl are substituted via one or more free radicals, they are, for example, mono-to-substituted, such as mono- , Two or three are substituted, especially 箪 —— or two are substituted. When I is a substituted phenyl radical, it is substituted via OR4 * SR4 and / or NR5 Rs plus M and a substituent When 01U, SR4 and medulla 5 Re form a 5- or 6-membered ring, the ring is formed by the radical IU, Rs or 1 ^, the ring has other substituents or has a benzene ring carbon atom, for example, may The following structure is obtained-11- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) -------- r ------ IT ------ φ (Please read first Note to fill out the back of this page) A7 V. invention is described in ((f)

N I RsN I Rs

.〇0,.〇0,

,0, 0

'0 在本發明申請案中，專有名詞〃雜芳基"表示未經取代的及經取代的自由基，例如2 —噻嗯基· ^'0 In the present application, the proper term "heteroaryl" means unsubstituted and substituted radicals, such as 2-thienyl. ^

(請先閲讀背面之注意事項再填寫本頁)(Please read the notes on the back before filling this page)

RsReN，RsReN,

S 其中Rs及Re為具有上述的定義，噻憩訂烯基*異苯並呋哺基，氧雜苞基（xanthenyl) phenoxathi iny1 其中X為s，绨經濟部中央樣準局貝工消費合作社印製或且RS具有上述的定義。實施例為吡唑基，睡唑基， «唑基，異唾唑基或異聘唑基。亦被包括在内者為，例如呋喃基，吡咯基，1，2，4_***基或5-貝雜環化合物類，其具有一稠合於其上之芳香性化合物，例如苄基咪唑基，苯並噻嗯基*苯並呋哺基*苯並聘 -12- 本紙張尺度適用中國國家揉準（CNS ) A4規格（210X297公釐）五、發明説明（唑基及苯並噻唑基 A7 十>Ί "雜芳基〃其他的實施例為砒啶基，特別是3—砒啶基S where Rs and Re have the above definitions, thioxenyl * isobenzofuryl, xanthenyl phenoxathi iny1 where X is s, Or RS has the above definition. Examples are pyrazolyl, doxazolyl, oxazolyl, isialazolyl or isoxazolyl. Also included are, for example, furyl, pyrrolyl, 1,2,4-triazolyl or 5-betheterocyclic compounds, which have an aromatic compound fused thereto, such as benzylimidazole Base, benzothienyl * benzofuryl * benzobenzyl-12- This paper size applies to China National Standard (CNS) A4 (210X297 mm) 5. Description of the invention (oxazolyl and benzothiazolyl A7 &" Heteroaryl " Other examples are pyridyl, especially 3-pyridyl

R4〇 NR4〇 N

其中R4具有上述的定義，為嘧啶基，. 哌嗪基，1，3，5 —三嗪基，2，4一，2，2-或2，3—二嗪基，吲哚嗪基，異吲哚基，吲哚基，吲唑基，嘌呤基，異喹啉基*喹啉基，吩嗥嗪基或吩嗪基。在此專利申請案中，專有名詞"雜芳基〃亦表示自由基硫黃嘌呤基，黃嘌呤基Where R4 has the above definition and is pyrimidinyl, piperazinyl, 1,3,5-triazinyl, 2,4-mono, 2,2- or 2,3-diazinyl, indolazinyl, iso Indolyl, indolyl, indazolyl, purinyl, isoquinolyl * quinolyl, phenazinyl or phenazinyl. In this patent application, the term "heteroaryl" also refers to the radical thioxanthine, xanthine

0 '00 '0

其中R (請先閲讀背面之注意事項再填寫本頁) 訂Of which R (Please read the notes on the back before filling this page) Order

Rs ，Re及b為具有上述的定義Rs, Re and b have the above definitions

Ο N 或憩醚基。每個雜芳基可攜有上述或在申請專利範圍第1項之取代基。線經濟部中央標隼局貝工消費合作杜印製樟腦基為Ο N or ether. Each heteroaryl group may carry a substituent as described above or within the scope of patent application No. 1. Produced by Shellfish Consumer Cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs

0 當Ri及1?2在合適時共同與C0基團，形成一 5—或6 -員環，例如為一環戊烷，環己烷，吡哺或锨啶環。可與該環稠合者，例如，亦為苯並，萘並，憩並，菲並或雑芳基 -13 本紙法尺度適用中國固家標準（CNS ) A4規格（210X297公釐） A7 B7 五、發明説明（/〇 ) 自由基，所形成的结構如0 When Ri and 1,2 are together with the CO group when appropriate, a 5- or 6-membered ring is formed, such as a cyclopentane, cyclohexane, pyrimidine or pyridine ring. Those that can be fused with this ring, for example, benzo, naphtho, benzo, phenanthrene or fluorenyl-13 This paper method is applicable to China Solid Standard (CNS) A4 (210X297 mm) A7 B7 5 、 Explanation of the invention (/ 〇) free radical, the structure formed is

(請先閲讀背面之注意事項再填寫本頁) --祛 --裝. 訂線· 線經濟部中央標準局員工消費合作社印製述的定義，在這些结構中芳香性環可攜帶進一步如前文或申請專利範圍第1項所定義之取代基。他們亦為，例如，四 . 氫萘，二氫憩，氫茚，苯並二氫吡喃，葬，氧雜葸（ xanthene)或硫氧雜趕（xanthene)環系統。當該環含有羰基圑時，可形成例如苯並輥，萘並醚或憩酮自由基。(Please read the notes on the back before filling out this page)-Dismantle-Install. Thread and Line • The definition printed by the Central Consumers Bureau of the Ministry of Economic Affairs and the Consumer Cooperatives. The aromatic ring can be carried further in these structures as described above. Or the substituent defined in item 1 of the scope of patent application. They are also, for example, tetralin, dihydrogen, indene, benzodihydropyran, burial, xanthene or xanthene ring systems. When the ring contains a carbonyl fluorene, for example, a benzo roll, a naphthyl ether or a ketone radical can be formed.

Ci — Cs烷趣基為，例如，甲醢基，乙醯基，丙酿棊，丁酿基或己醢基，特別是乙醢基。 -14- 本紙張尺度適用中國國家橾準（CNS ) A4规格（210X297公釐）一 ~~ 經濟部中央樣準局負工消费合作社印製 A7 B7 五、發明説明（// ) h 烷氧基為，例如，甲氧基，乙氧基，丙氧基及丁氧基，在具有超過兩個碳原子之烷氧基基團中的烷基自由基有可能為分枝的。 C2 -Cs烷氧基羰基為（Ci 一“烷基）—0— c(o) -，其中Ci _Cs烷基如前文定義達到合適的碳原子數目。實例為甲氧基羰基，乙氧基羰基*丙氧基羰基，丁氧基羰基或戊基氧羰基'在具有超過兩個碳原子之烷氧基基團中的烷基自由基有可能為分枝的。Ci—Cs alkyl is, for example, methylamidino, ethylamidino, propylamino, butylamino or hexamethyl, especially ethylacetyl. -14- This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 1 ~~ Printed by A7 B7, Central Consumers ’Cooperative Cooperative of the Ministry of Economic Affairs 5. Description of Invention (//) For example, methoxy, ethoxy, propoxy, and butoxy, alkyl radicals in alkoxy groups having more than two carbon atoms may be branched. C2 -Cs alkoxycarbonyl is (Ci-"alkyl"-0-c (o)-, where Ci_Cs alkyl as defined above reaches the appropriate number of carbon atoms. Examples are methoxycarbonyl, ethoxycarbonyl * The alkyl radical of propoxycarbonyl, butoxycarbonyl or pentyloxycarbonyl 'in an alkoxy group having more than two carbon atoms is likely to be branched.

Cl — Cl 〇齒烧基及Cl — C4齒焼基為Cl — Cl .〇 — 及Ci -C4 一烷基，其經由鹵素進行單——或多—取代的，Ci -Ci。一及Ci — C4 一烷基，例如，具有上述的定義。在烷基自由基上具有例如，自一至三個或一個或二個鹵素取代基。實施例為氮甲基，三氯甲基，三氟甲基或2_ 溴丙基，特別是三氟甲基或三氯甲基。鹵素為氟，氛，溴或碘，特別是氢或氟，偏好為氟。在一基團S(0) n — Ce — Cl 〇芳基中，其可為未經取代的或經由—Ci 2烷基加以取代的，該芳基自由基為苯基，甲苯基，十二烷基磺醢基琪1 一或2 —萘基。 -15- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） I 裝 i 線 (請先閱讀背面之注意事項再填寫本頁) A7 B7 五、發明説明（/〆) 苯基一 Cl _C3烷基為，例如，苄基，2—苯基乙基 3_苯基丙基，α —甲基苄基或二甲基苄基，特別是苄基氣二亞苯基為當RS及Re共同與他們所連接的氮原子共同形成一 5 — ，6 —或7 —員環，其可由一〇 —或由一 NR4 —加以中斷，例如得到下列结構 (請先聞讀背面之注意事項再填寫本頁)Cl — Cl 0 alkynyl and Cl — C4 dentate are Cl — Cl. 〇 — and Ci-C 4 monoalkyl, which are mono- or poly-substituted via halogen, Ci-Ci. And Ci—C4 monoalkyl, for example, have the definitions described above. The alkyl radical has, for example, from one to three or one or two halogen substituents. Examples are nitrogen methyl, trichloromethyl, trifluoromethyl or 2-bromopropyl, especially trifluoromethyl or trichloromethyl. Halogen is fluorine, atmosphere, bromine or iodine, especially hydrogen or fluorine, and fluorine is preferred. In a group S (0) n-Ce-Cl0aryl, which may be unsubstituted or substituted via -Ci 2 alkyl, the aryl radical is phenyl, tolyl, twelve Alkylsulfonyl 1- or 2-naphthyl. -15- This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297mm) I installed i cable (Please read the precautions on the back before filling this page) A7 B7 V. Description of invention (/ 〆) Phenyl A Cl_C3 alkyl group is, for example, a benzyl group, a 2-phenylethyl 3-phenylpropyl group, an α-methylbenzyl group or a dimethylbenzyl group, especially a benzyl gas diphenylene group when RS And Re together with the nitrogen atom to which they are connected form a 5—, 6—or 7—membered ring, which can be interrupted by 10—or NR4—for example, to obtain the following structure (please read the precautions on the back first) (Fill in this page again)

N ηN η

N • R5N • R5

NN

Q 訂經濟部中央標準局貝工消費合作社印裝偏好的組成物為其中在式I之化合物類中：Ri為苯基，其经由（^ - Cs烷基，苯基，0R4 ，SR4及/或經由NR 5 Re加K取代；取代基OIU ，SR4及NR5 Rs有可能形成5 —或6 —員環，該環的形成係藉由自由基R4 ，RS及/或R 6 ，環上具有進一步的取代基或具有苯環上碳原子之一。進一步有利的組成物為其中在式I之化合物類中：Ri 為雜芳基，其為未經取代的或經由Ci _C6烷基，苯基， OR. SR4及/或經由HRS R6進行軍——或多-取代，取線 16- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（/5) 代棊0R4 ，SR4及NR5 R6有可能形成5-或6-員環，該環的形成係藉由自由基R4 ，Rs及/或R6 ，環上具有進一步的取代基或具有雜芳基環上碳原子之一。特別應提到的組成物為其中在式I之化合物類中：為C2 - Cs烷氧基羰基* CN* Ci -C4鹵烷基，S (0) nC i _C6烷基，或為未經取代的或為（^ — Ci 2烷基一取代的 S ( 0) η — C6 - C i 〇芳棊。偏好的組成物為其中在式I之化合物類中：1U為Ci _ C6烷基，其為未經取代的或經由OH，Ci 一（：4烷氧基，C i—Ci 2烷基磺醢基，苯基磺醢基，（4一甲基苯基）磺醢基及/或經由Cz - C6烷醢基加K取代且其可額外地被一 0 —中斷。有利的組成物類為那些在式I化合物類中m為〇且X為1者 0 偏好的組成物為其中在式I之化合物類中：R3為Cl -Ci s烷基，Ci -Ci。鹵烷基，或苯基，其為未經取代的或经由鹵素，N〇2 ，C , — C4鹵烷基，C i - C t 2烷基， 01U ，C00R7及/或經由- OCO—Ci — c4烷基加Μ取代。本紙張尺度適用中國國家揉準（CNS ) A4規格（210X297公釐） ----------1------IT-------多 (請先閱讀背面之注意事項再填寫本頁) A7 B7 五、發明说明（/+) 偏好的組成物為其中在式I之化合物類中：in為0且X為1 ，為3，4一二甲氧基苯基，3，4_二（甲基硫）苯基， 3—甲氧基一 4 一甲基硫苯基R2為CN或4 -氰基苯基，且R3 為苯基，4 一甲基苯基，4 一甲氧基苯基，3_三氟甲基苯基，4一氛苯基，甲基，異丙基，n —辛基，2，4，6— （三異丙基）一苯基，4 一硝基苯碁，2，4，6—三甲基苯基或十二烷基苯基或及1?2共同形成一荛系統其中該芳香性環經由甲氧基或羥基乙基硫基團進行取代。本發明亦相關於根據申請專利範圍第1項之式I化合物類作為供可在酸的作用下被交叉聪结的化合物類之光起動劑類的用途及/或作為供溶解性在酸的作用下會改變的化合物類之溶解性抑制劑類的用途。在可光交叉聯结的組成物類中，肟磺酸酯類作為沉潛性熟化觸媒類：當以光進行輻射時，他們可以釋出酸而催化該交叉聯结反應。此外，經由輻射釋出的酸可，洌如，催化合適的酸一敏感性保護性基團類自一聚合物结構脫離*或催化在聚合物骨幹上含有酸一敏感性基團類的聚合物類的切割。其他的應用為*例如，及於PH改變或經，例如，酸-敏感性保護性基團保護之色素的溶解度改變之色影一轉變系統。 -18- 本紙張尺度逋用中國國家橾準（CNS ) A4規格（210X297公釐） ---------^------,訂------终 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（/ f ) 最後，在一水性一驗性顯影劑中不易溶解的肟磺酸酯類可K經由光誘發性轉變成為游離酸，因而在顯影劑中爱成可溶解的，且得到的结果指出，他們可與合適的薄層一形成樹脂類聯用以作為溶解性抑制劑類。可以經由酸催化進行交叉聯结的樹脂類為，例如，多官能性醇類或羥基一基團一内含性丙烯性及聚酯樹脂類的混合物類，或部份地被水解的聚乙烯基乙醛類或具有多官能性乙醛衍生物類之聚乙烯基酵類。在特定條件下，例如乙醛-官能基化樹脂類之酸-催化性自行縮合反應亦為可能的情形。此外，肟磺酸酯類可被用於，例如，作為供矽氧烷基團一内含性樹脂類之光一可活化的硬化劑類。那些樹脂類可，例如，或經遇藉由酸催化性水解作用之自行一縮合作用或可K樹脂的第二種成分進行交叉聪结，如一多官能性酵，一羥基一基匾一内含性丙烯性或聚酯樹脂，一部份地被水解的聚乙烯基乙醛或一聚乙烯基醇。此棰型態的聚矽氧烷類的聚縮合作用見述於，例如，J.J.Lebrun，H. Psde ，Comprehensive Polymer Science， Volume 5，第 593頁，Pergamon Press， Oxford » 1989° 在那些反應中亦喜好K長波長光進行輻射之被釋出的 -19- 本紙張尺度適用中國國家橾準（CNS ) A4規格（2丨0><297公釐） (請先閩讀背面之注意事項再填寫本頁) % 線 A7 B7 五、發明説明（/^ 酸。令人驚異地，現已發現一些肟磺酸酯類即而以超過390 微毫米之長波長光進行輻射，也能夠釋出酸。本發明因此亦相關於式la化合物類作為供波長超過390 撤奄米之輻射之感光性酸提供者的用途’ (請先閱讀背面之注意事項再填寫本頁) R; 〇 II -C- -C=N-〇-S〇2 I 2 r2 •r3 ⑽ 訂其中m為0或1且x為1或2 ; 線經濟部中央標準局員工消費合作社印製Q. The composition preferred by the Central Standards Bureau of the Ministry of Economic Affairs of Shellfish Consumer Cooperatives is among the compounds of formula I: Ri is phenyl, which is via (^ -Cs alkyl, phenyl, OR4, SR4 and / or Substituted by NR 5 Re plus K; the substituents OIU, SR4 and NR5 Rs may form a 5- or 6-membered ring. The ring is formed by the radicals R4, RS and / or R6. A substituent or one of the carbon atoms on the benzene ring. A further advantageous composition is where in the compounds of formula I: Ri is heteroaryl, which is unsubstituted or via Ci_C6 alkyl, phenyl, OR SR4 and / or military through HRS R6-or more-replace, take line 16-This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm) Printed by A7 B7, Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs 5. Description of the invention (/ 5) Substituting 棊 0R4, SR4 and NR5 R6 may form a 5- or 6-membered ring. The ring is formed by radicals R4, Rs and / or R6, and the ring has further substitution. Or having one of the carbon atoms on the heteroaryl ring. Compositions which should be mentioned in particular are the compounds of formula I In the category: C2-Cs alkoxycarbonyl * CN * Ci -C4 haloalkyl, S (0) nC i _C6 alkyl, or unsubstituted or (^ — Ci 2 alkyl monosubstituted S (0) η — C6-C i 〇 aryl. Preferred composition is among the compounds of formula I: 1U is Ci_C6 alkyl, which is unsubstituted or via OH, Ci a (: 4 alkoxy, Ci-Ci 2 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or substituted via Cz-C6 alkylsulfonyl plus K and its amount The field is interrupted by a 0. Advantageous compositions are those where m is 0 and X is 1 among the compounds of formula I. Preferred compositions are where among the compounds of formula I: R3 is Cl-Ci s alkane Ci, Ci-Ci, haloalkyl, or phenyl, which are unsubstituted or via halogen, No2, C,-C4 haloalkyl, Ci-Ct 2 alkyl, 01U, C00R7 and / Or replaced by -OCO-Ci-c4 alkyl plus M. This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) ---------- 1 ------ IT ------- Multiple (please read the notes on the back before filling this page) A7 B7 V. Description of the invention ( / +) The preferred composition is among the compounds of the formula I: in is 0 and X is 1, 3,4-dimethoxyphenyl, 3,4-bis (methylthio) phenyl, 3-methoxy-4 methylthiophenyl R2 is CN or 4-cyanophenyl, and R3 is phenyl, 4-methylphenyl, 4-methoxyphenyl, 3-trifluoromethyl Phenylphenyl, 4-aminophenyl, methyl, isopropyl, n-octyl, 2,4,6- (triisopropyl) monophenyl, 4-mononitrophenylfluorene, 2,4,6 —Trimethylphenyl or dodecylphenyl or 1 and 2 together form a hydrazone system in which the aromatic ring is substituted via a methoxy or hydroxyethylthio group. The invention also relates to the use of the compounds of formula I according to item 1 of the scope of the patent application as light starters for compounds that can be cross-linked under the action of acids and / or for the role of solubility in acids The use of solubility inhibitors of compounds that will change is as follows. Among the photo-crosslinkable compositions, oxime sulfonates are used as latent ripening catalysts: when irradiated with light, they can release acid to catalyze the cross-linking reaction. In addition, the acid released via radiation can, for example, catalyze the removal of suitable acid-sensitive protective groups from a polymer structure * or catalyze polymers containing acid-sensitive groups on the polymer backbone Class of cutting. Other applications are * for example, color-shift systems that change pH or change the solubility of pigments protected by acid-sensitive protective groups. -18- This paper uses China National Standard (CNS) A4 size (210X297 mm) --------- ^ ------, order ------ final (please first Read the notes on the back and fill in this page) A7 B7 printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (/ f) Finally, the oxime sulfonates that are not easily dissolved in a water-based test developer can K is converted into a free acid by photo-induced conversion, so it becomes soluble in the developer, and the results obtained indicate that they can be combined with a suitable thin layer to form a resin class for use as a solubility inhibitor. Resins that can be cross-linked via acid catalysis are, for example, polyfunctional alcohols or a mixture of hydroxyl-group-containing acrylic and polyester resins, or partially hydrolyzed polyvinyl groups Acetaldehydes or polyvinyl enzymes with polyfunctional acetaldehyde derivatives. Under certain conditions, for example, acid-catalytic self-condensation reactions of acetaldehyde-functionalized resins are also possible. In addition, oxime sulfonates can be used, for example, as light-activatable hardeners for siloxane groups-inclusive resins. Those resins can, for example, undergo self-condensation through acid-catalyzed hydrolysis or cross-linking with a second component of K resin, such as a multifunctional enzyme, a hydroxyl group, a plaque, and a compound Containing acrylic or polyester resin, partially hydrolyzed polyvinyl acetaldehyde or a polyvinyl alcohol. The polycondensation of this type of polysiloxane is described in, for example, JJ Lebrun, H. Psde, Comprehensive Polymer Science, Volume 5, p. 593, Pergamon Press, Oxford »1989 ° Also in those reactions I like the release of K long-wavelength light -19- This paper size applies to China National Standard (CNS) A4 specification (2 丨 0 > < 297 mm) (Please read the notes on the back before filling This page)% line A7 B7 V. Invention description (/ ^ acid. Surprisingly, it has been found that some oxime sulfonates can release acid even when irradiated with long-wavelength light exceeding 390 micrometers. The present invention is therefore also related to the use of compounds of formula la as photosensitive acid providers for radiation with a wavelength in excess of 390 millimeters' (Please read the precautions on the back before filling this page) R; 〇II -C-- C = N-〇-S〇2 I 2 r2 • r3 订 Set m as 0 or 1 and x as 1 or 2; Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Line Economy

'為苯基，其經由一種或多種自由基加以取代，該自由基可為- Cs烷基，苯基，0R4 ，SIU及/或NR5 R 6 ;取代基0R4 ，SR4及NR5 R6有可能形成5-或6 —員環，該環的形成係藉由自由基R4 ，RS及/或R6 ，環上具有進一步的取代基或具有苯環上碳原子之一，或Ri '為萘基，憩基或菲基；自由基萘基，趕基及菲基為未經取代的或經由Ci -Cs烷基，苯基，OR4 ，SR4及/或經由HR5 R6 加Μ軍——或多重一取代；取代基OR, -20- 本紙張尺度適用t國國家橾準（CNS ) A4規格（210X 297公釐） SR4 及 NRS 有經濟部中央標隼局貝工消費合作社印裳 A7 £7_ 五、發明説明（q) 可能形成5—或6 —員環，該環的形成係經由自由基R4 ，及 /或Rs ，環上具有進一步的取代基或具有萘基，趕基或菲基環上碳原子之一，或！^ '為一雜芳基自由基，其為未經取代的或经由C ! 一 Cs烷基，苯基，0R4 ，SR4及/或經由NRS Rs加以取代；取代基OiU ，SR4及^5 Rs有可能形成5—或6 —員環，該環的形成係藉由自由基R4 ，R5& /或R6 ，環上具有進一步的取代基或具有雜芳基環上碳原子之一； R2具有'定義之一或為未經取代的苯基，Ci — C e —烷醢基，苄醢基，其為未經取代的或經由_Ce烷基，苯基，0R4 ，SR4及/或經由NRs 加以取代，C2 _C6烷氧基羰基，苯氧基羰基，R5 Re N，嗎啉基*帮啶基，CH，Ci - C4鹵烷基，S (0) nCt — C6烷基，未經取代的或Ci — h 2烷基一取代的S(0) η — C6 - Ci 2芳基，S02 0-Ci _C6 烷基，S02 0— Cs — C! 〇芳基或 NHC0NH2 ，其中n為1或2 ; 或R !'及Rz ，若合適時則共同與C 0基團，形成一 5 -或6 —員環，其為未經取代的或經由Ci 一 C6烷基，苯基，〇“ ，sr4或經由MRS R6加以取代且其可額外地被0，S, NRS及/或被C0加K中斷且一種或多種苯並自由基可與其铜合ί -21- 本紙張尺度適用中國國家揉準（CNS > A4规格（2丨0X297公釐） ---------,1^------IT------A (請先閲讀背面之注意事項再填寫本頁)'Is phenyl, which is substituted via one or more free radicals, which may be -Cs alkyl, phenyl, OR4, SIU, and / or NR5 R6; the substituents OR4, SR4, and NR5 R6 may form 5 -Or 6-membered ring, the ring is formed by the radical R4, RS and / or R6, the ring has a further substituent or has one of the carbon atoms on the benzene ring, or Ri 'is a naphthyl group, a restyl group Or phenanthryl; radical naphthyl, cyclyl, and phenanthryl are unsubstituted or via Ci-Cs alkyl, phenyl, OR4, SR4, and / or via HR5 R6 plus MH- or multiple one substitution; substitution OR, -20- This paper size is applicable to the national standard (CNS) A4 size of the country (210X 297 mm) SR4 and NRS. There is a seal A7 of the shelling consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. £ 7_ 5. Description of the invention ( q) May form a 5- or 6-membered ring, the ring is formed via radicals R4, and / or Rs, with further substituents on the ring or with one of the carbon atoms on the naphthyl, fluorenyl or phenanthryl ring ,or! ^ 'Is a heteroaryl radical, which is unsubstituted or substituted via C! -Cs alkyl, phenyl, OR4, SR4, and / or via NRS Rs; the substituents OiU, SR4, and ^ 5 Rs have May form a 5- or 6-membered ring, the ring is formed by the radical R4, R5 & or R6, the ring has further substituents or has one of the carbon atoms on the heteroaryl ring; R2 has the definition One is unsubstituted phenyl, Ci-Ce-alkylfluorenyl, benzamidine, which is unsubstituted or substituted via _Ce alkyl, phenyl, OR4, SR4 and / or via NRs , C2 _C6 alkoxycarbonyl, phenoxycarbonyl, R5 Re N, morpholinyl * pyridyl, CH, Ci-C4 haloalkyl, S (0) nCt — C6 alkyl, unsubstituted or Ci — H 2 alkyl-substituted S (0) η — C6-Ci 2 aryl, S02 0-Ci — C6 alkyl, S02 0—Cs — C! 〇aryl or NHC0NH2, where n is 1 or 2; or R! 'And Rz, if appropriate, together with the C 0 group to form a 5- or 6-membered ring, which is unsubstituted or via Ci-C6 alkyl, phenyl, 〇 ", sr4 or via MRS R6 is replaced and it can additionally 0, S, NRS and / or interrupted by C0 plus K and one or more benzo radicals can be combined with its copper -21- This paper size is applicable to Chinese national standards (CNS > A4 size (2 丨 0X297 mm) ---------, 1 ^ ------ IT ------ A (Please read the notes on the back before filling this page)

A7 B7___ 五、發明説明（/f) R3 *當X為1時，為Ci — Ci 8烷基，苯基一(^ -C3 烷基，樺腦基，Ci _C1o鹵烷基，苯基，萘基，憩基或菲基；自由基苯基，萘基，趕基及菲基為未经取代的或经由一種或多種自由基鹵素，Ci — C4鹵烷基，CN，N〇2 ，C 1 一 Ci e 燒基 ’ OR4 ，COOR7 ，一 OCO— Ci — C4 烧基， S02 0R7及/或經由Rs N加κ取代，或R3 ，當X為2時，為c2 _Cl2亞烷基，亞苯基，亞萘基，二亞苯基或氧二亞苯基；自由基亞苯基，亞萘基，，二亞苯基及氧二亞苯基為未經取代的或經由c i 一 C i 2烷基加以取代； R4為氫，Ci —Ci 2烷基，其為未經取代的或經由苯基，OH，Ci 一 C4烷氧基，Ci - Ci 2烷基磺醢基，苯基磺醢基，（4一甲基苯基）磺醢基及/或經由Ct 一（：6烷醮基加Μ取代且其額外地被一〇—中蹶；A7 B7___ 5. Description of the invention (/ f) R3 * When X is 1, Ci—Ci 8 alkyl, phenyl-(^-C3 alkyl, betulinyl, Ci_C1o haloalkyl, phenyl, naphthalene Radical, aryl or phenanthryl; radical phenyl, naphthyl, cyclyl and phenanthryl are unsubstituted or via one or more free radical halogens, Ci-C4 haloalkyl, CN, No2, C1 One Ci e alkyl group OR4, COOR7, one OCO-Ci-C4 alkyl group, S02 0R7 and / or Rs N plus κ substitution, or R3, when X is 2, it is c2_Cl2 alkylene, phenylene , Naphthylene, diphenylene or oxydiphenylene; radical phenylene, naphthylene,, diphenylene and oxydiphenylene are unsubstituted or via ci-C i 2 alkane R4 is hydrogen, Ci—Ci 2 alkyl, which is unsubstituted or via phenyl, OH, Ci—C4 alkoxy, Ci—Ci 2 alkylsulfonyl, phenylsulfonyl , (4-methylphenyl) sulfofluorenyl and / or substituted via Ct- (6 alkylfluorenyl plus M and it is additionally substituted with 10-methane;

R5及R6彼此獨立為氫或Ci 一（^ 2烷基，其為未經取代的或經由OH，Ci 一（：4烷氧基，h -Ci 2烷基磺醯基，苯基磺醯基，（4一甲基苯基）一磺醮基及/或經由C -22- 本紙張尺度適用中國國家揉準（CNS ) A4规格（210X297公釐） (請先閱讀背面之注f項再填寫本頁) 訂經濟部中央橾準局貝工消费合作社印製經濟部中央標準局員工消费合作社印装 A7 B7__ 五、發明説明（// )R5 and R6 are each independently hydrogen or Ci- (2 alkyl, which is unsubstituted or via OH, Ci- (4 alkoxy, h-Ci 2 alkylsulfonyl, phenylsulfonyl) , (4-methylphenyl) -sulfofluorenyl and / or via C-22- This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) (Please read the note f on the back before filling (This page) Order Printed by the Central Bureau of Standards of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Printed by the Consumers' Cooperative of A7 B7__ V. Description of Invention (//)

! 一（：6烷醢基加Μ取代且其可額外地被一 0 —所中斷，或R s及Rs為苯基，Ci — Ce烷醯基，苄醢基，h -（：6烷基磺醢基，苯基磺酵[基，（4一甲基苯f)磺醢基，萘基磺醢基，蒽基磺醢基或菲基磺醣基，或Rs及R6共同與他們所連结的氮原子，形成一 5-，6 -或7 -員環，其可由一 0 — 或由_NR4 -加K中斷；且R7為Ci 一 Ci z烷基，其為未經取代的或經由0 Η及 /或由Ci 一（：4烷氧基加Κ取代，且其可額外地被一 0—加 Μ中斷。特別有利使用的式la之化合物類中：'為苯基，其經由Ci -C6烷基，苯基，OfU ，SIU及/或經由NRS Rs 加以取代；取代基〇R4 * SR4及NR5 R6有可能形成5—或6 —員環，該環的形成係藉由自由基IU ，Rs及/或“，環上具有進一步的取代基或具有苯環上碳原子之一。! ((6alkylalkyl plus M substituted and it may be additionally interrupted by a 0-, or Rs and Rs are phenyl, Ci-Cealkylalkyl, benzamidine, h-(: 6-alkyl Sulfonyl, phenylsulfonyl [phenyl, (4-methylbenzenef) sulfonyl, naphthylsulfonyl, anthracenylsulfonyl or phenanthrenesulfonyl, or Rs and R6 are linked to them together The bound nitrogen atom to form a 5-, 6- or 7-membered ring, which can be interrupted by a 0 — or _NR4 — plus K; and R7 is Ci — Ci z alkyl, which is unsubstituted or via 0 Η and / or is substituted by Ci- (4 alkoxy plus K, and it can be additionally interrupted by a 0-plus M. Among the compounds of formula la which are particularly advantageously used: 'is phenyl, which is passed via Ci -C6 alkyl, phenyl, OfU, SIU and / or substituted by NRS Rs; the substituents OR4 * SR4 and NR5 R6 may form a 5- or 6-membered ring, the ring is formed by the radical IU Rs and / or ", have further substituents on the ring or have one of the carbon atoms on the benzene ring.

進一步有利使用的式la之化合物類中：Ri '為雜芳基 *其為未經取代的或經由Ci —Cs烷基，苯基，0R4 ，SR 4及/或經由NR5 Rs進行軍一一或多一取代；取代基0R4 ，SR4及NRS Rs有可能形成5 —或6—貝環，該環的形成係藉由自由基R4 ，1^及/或R6 ，環上具有進一步的取代基或具有雜芳基環上碳原子之一。 -23- 本紙張尺度適用中國國家橾準（CNS ) A4说格（210X297公釐） -----------装------訂------線 (请先閲讀背面之注意事項再填寫本頁) 五、發明説明（^) A7 B7 本發明亦相關於式lb之新穎肟磺酸酯類 R, one -C=N—〇—SOr- i 2 其中m為0或1且x為1或 (lb) 經濟部中央樣準局負工消費合作社印製Among the compounds of the formula la further advantageously used: Ri 'is heteroaryl * which is unsubstituted or via Ci-Cs alkyl, phenyl, OR4, SR 4 and / or via NR5 Rs More than one substitution; the substituents OR4, SR4 and NRS Rs may form a 5- or 6-shell, the ring is formed by the radicals R4, 1 ^ and / or R6, with further substituents on the ring or with One of the carbon atoms on a heteroaryl ring. -23- This paper size is applicable to China National Standards (CNS) A4 grid (210X297 mm) --------------------------- Order Read the notes on the back before filling in this page) 5. Description of the invention (^) A7 B7 The present invention is also related to the novel oxime sulfonates R of formula lb, one -C = N—〇—SOr- i 2 where m 0 or 1 and x is 1 or (lb) Printed by the Consumer Goods Cooperative, Central Bureau of Standards, Ministry of Economic Affairs

Ri 〃為苯基，其經由一種或多種自由基加K取代，該自由基可為Ci - Cs烷基，苯基，0R4 ，SR4及/或NRs R 6 ;取代基〇“ ，SR4及NRS Rs有可能肜成5-或6-員環，該環的形成係藉由自由基IU ，Rs及/或K6 *環上具有進一步的取代基或具有苯環上碳原子之一，或Ri "為萘基，憩基或菲基；自由基萘基*截基及菲基為未經取代的或經由Ct - Ce烷基，苯基，0R4 ，SR4及/或经由NR5 Rs 加以單——或多重-取代；取代基01U ，SR4及NR5 Rs有可能形成5 —或6—員環，該環的形成係經由自由基R4 ，R s及/或Re ，環上具有進一步的取代基或具有萘基，憩基或菲基環上碳原子之一，或Ri "為一雜芳基自由基，其為未經取代的或經由C i 一 C6烷基，苯基，0R4 ，SR4及/ 或經由NRS R6加以取代；取代基〇R4 ，S1U及NRS R6有可能形成5—或6—員環，該環的形成係藉由自由基R4 ，R -24- I— I I n I I I 裝 I I I 訂 I I 線 (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）經濟部中央標準局貝工消费合作社印裂 A7 B7_ 五、發明説明（vh 5及/或，環上具有進一步的取代基或具有雜芳基環上碳原子之一，其條件為R:"不為未取代的睡嗯基；Ri 〃 is phenyl, which is substituted via one or more free radicals plus K, which radicals may be Ci-Cs alkyl, phenyl, OR4, SR4 and / or NRs R 6; substituents ″, SR4 and NRS Rs It is possible to form a 5- or 6-membered ring, the ring is formed by the radical IU, Rs and / or K6 * ring has further substituents or has one of the carbon atoms on the benzene ring, or Ri " Is naphthyl, alkyl or phenanthryl; radical naphthyl * truncated and phenanthryl are unsubstituted or mono- via Ct-Ce alkyl, phenyl, OR4, SR4 and / or via NR5 Rs-or Multi-substitution; the substituents 01U, SR4 and NR5 Rs may form a 5- or 6-membered ring, the ring is formed via the radicals R4, Rs and / or Re, with further substituents on the ring or with naphthalene One of the carbon atoms on the aryl, aryl, or phenanthryl ring, or Ri " is a heteroaryl radical, which is unsubstituted or via C i -C6 alkyl, phenyl, OR4, SR4, and / or Substituted by NRS R6; the substituents OR4, S1U and NRS R6 may form a 5- or 6-membered ring, the ring is formed by the radicals R4, R-24-I-II n III II I order II line (please read the notes on the back before filling this page) This paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) The Central Standards Bureau of the Ministry of Economic Affairs of the Bayer Consumer Cooperative printed A7 B7_ V. Invention Explanation (vh 5 and / or, there is a further substituent on the ring or one of the carbon atoms on the heteroaryl ring, provided that R: " is not an unsubstituted sulphone group;

Rz具有Ri "定義之一或為未經取代的苯基’ C: - C 6 _烷醢基，苄醢基，其為未經取代的或經由Ci 一（：6烷基，苯基，0R4 ，SR4及/或經由NRS Re加以取代，C2 _CS烷氧基羰基，苯氧基羰基，Rs Re N，嗎啉基，哌啶基，CN* C! _C4鹵烷基，S (0) nC! -Cs烷基，未經取代的或Ci - Ci 2烷基一取代的S(0) n — C6 -C: 2芳基 * S〇2 〇—Ci — C6 燒基* S〇2 〇_Cs — Ci 〇芳基或 NHCONH2 ，其中n為1或2 ; 或Ri 〃及R2 ，若合適時則共同與C0基團，形成一 5 — 或6—員環，其為未經取代的或經由一（：6烷基，苯基，〇R4 ，SR4或經由NR5 Rs加以取代且其可額外地被0，S， NRs及/或被C0加K中斷且一種或多種苯並自由基可與其稠合；Rz has one of Ri " definitions or is unsubstituted phenyl 'C: -C 6 -alkylfluorenyl, benzamidine, which is unsubstituted or via Ci- (6 alkyl, phenyl, 0R4, SR4 and / or substituted via NRS Re, C2_CS alkoxycarbonyl, phenoxycarbonyl, Rs Re N, morpholinyl, piperidinyl, CN * C! _C4 haloalkyl, S (0) nC ! -Cs alkyl, unsubstituted or Ci-Ci2 alkyl mono-substituted S (0) n — C6 -C: 2aryl * S〇2 〇—Ci—C6 alkyl group * S〇2 〇_ Cs — Ci 〇aryl or NHCONH2, where n is 1 or 2; or Ri 〃 and R2, if appropriate, together with the C0 group to form a 5- or 6-membered ring, which is unsubstituted or via Mono (: 6 alkyl, phenyl, OR4, SR4 or substituted by NR5 Rs and it may be additionally interrupted by 0, S, NRs and / or C0 plus K and one or more benzo radicals may be condensed with it合； He;

Rs ，當X為1時，為C! —Ci 8烷基，苯基—C! -C3 烷基，樟腦基，Ci -C10鹵烷基，苯基，萘基，憩基或菲基；自由基苯基，萘基，憩基及菲基為未經取代的或經由一種或多種自由基鹵素，Ci - C4鹵烷基，CN，N〇2 ，C 1 — Ci 6 烷基，〇R4 ，COOR7 ，一OCO-Ci 烷基， -25- 本紙張尺度逋用中國國家搮準（CNS > A4规格（210X297公釐） I I 於訂線 (請先W讀背面之注意事項再填寫本頁)Rs, when X is 1, C! -Ci 8 alkyl, phenyl-C! -C3 alkyl, camphor, Ci-C10 haloalkyl, phenyl, naphthyl, aryl or phenanthryl; free Phenyl, naphthyl, aryl and phenanthryl are unsubstituted or via one or more free radical halogens, Ci-C4 haloalkyl, CN, No2, C1-Ci6 alkyl, OR4, COOR7, an OCO-Ci alkyl group, -25- This paper size is in accordance with China National Standards (CNS > A4 size (210X297 mm)) II To order (please read the precautions on the back before filling this page)

五、發明説明（T/M A7 B7V. Description of the invention (T / M A7 B7

SO2 OR7及/或經由Rs R6 N加Μ取代其條件為當R3為苯基，3—氛苯基或4 一甲基苯基時，作為甲氧基一取代之苯環之Ri必在環上含有至少一個進一步的取代基，然而該取代基不為甲氧基或甲基，且其條件為沒有兩個取代基OIU 形成一1，3 —二氧伍環，或R3 ，當X為2時，為SO2 OR7 and / or substitution by Rs R6 N plus M. The condition is that when R3 is phenyl, 3-phenyl or 4-methylphenyl, Ri as methoxy-substituted benzene ring must be on the ring Contains at least one further substituent, but the substituent is not methoxy or methyl, provided that no two substituents OIU form a 1,3-dioxo ring, or R3 when X is 2 ,for

-C 亞烷基，亞苯基，亞萘基，一二亞苯基或氧二亞苯基；自由基亞苯基，亞萘基-C alkylene, phenylene, naphthylene, diphenylene or oxydiphenylene; radical phenylene, naphthylene

二亞苯基及氧二亞苯基為未經取代Diphenylene and oxydiphenylene are unsubstituted

的或經由C i — C 烷基加Μ取代；經濟部中央標準局貝工消费合作社印策 R4為氫，Ci —Ci 2烷基，其為未锂取代的或經由苯基，OH，Ci _C4烷氧基，Ci — Ci 2烷基碩醢基，苯基磺醢基，（4 一甲基苯基）磺醢基及/或經由Ci-Cs烷醯基加以取代且其額外地被一0 —中斷；Or substituted by C i -C alkyl plus M; the policy of the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, R4 is hydrogen, Ci-Ci 2 alkyl, which is unlithium substituted or via phenyl, OH, Ci_C4 Alkoxy, Ci — Ci 2 alkyl sulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or substituted via Ci-Cs alkylsulfonyl and it is additionally substituted by a 0 — Interrupt;

Rs及1彼此獨立為氫或（^ — Ci 2烷基，其為未經取代的或經由OH，Ci _C4烷氧基，Ci — Ci 2烷基磺醢基，苯基磺醯基，（4一甲基苯基）_磺醯基及/或經由C ! —Cs烷醢基加以取代且其可額外地被一〇 —所中斷，或R -26- 本紙張尺度逋用中國國家揉準（CNS ) A4规格（2丨OX297公釐） I 裝訂 II 線 (請先閱讀背面之注意事項再填寫本頁) 經濟部中夬橾準局貝工消费合作杜印裝 A7 _B7_ 五、發明説明（^*1) S及R6為苯基，Ci 一06烷醢基，苄醢基，Ci —c6烷基磺醢基，苯基磺醢基，（4 一甲基苯基）磺醢基，蔡基磺醱基，蒽基磺醢基或菲基磺醢基，或R5及R6 ，共同與他們所埋结的氮原子，形成一 5—，6—或7—員環，其可由一 0 一或由一 NR4—加Μ中斷；且R7為h 2烷基，其為未經取代的或經由Ο Η及 /或由Ci - C4烷氧基加以取代，且其可額外地被—0—加以中斷。特別有利的是化合物α- （甲基磺醢基氧亞胺基）一3 ，4一二甲氧基一苄基氰化物，c(一（4一十二烷基苯基磺睡基氧亞胺基）—3，4 —二甲氧基苄基氣化物或α — （4 一甲基-苯基磺藤基氧亞胺基）一 4一硫甲基苄基氰化物，α 一（2—丙基磺醢基氧亞胺基）一 3，4一二甲氧基苄基氰化物，α —(苯基磺醢基氧亞胺基）一 3，4一二甲氧基苄基氰化物，(4 -甲氧基苯基磺皤基氧亞胺基）一 3，4_ 二甲氧基苄基氰化物，α — （2，4，6—參（異丙基）一苯基一磺醢基氧亞胺基）一 3，4_二甲氧基苄基氰化物，《 -(η—辛基磺醢基氧亞胺基）一 3，4一二甲氧基苄基氰化物，α — （4 一氛苯基磺釀基氧亞胺基）一 3· 4—二甲氧基苄基氰化物，a — (3-三氟甲基苯基磺醢基氧亞胺基）_ 3，4 —二甲氧基苄基氰化物，α —(甲基一磺醢基氣亞胺 -27- 本紙張尺度逋用中國國家揉準（CNS > Α4規格（210Χ297公釐） (請先閲讀背面之注意事項再填寫本頁) -裝. 訂經濟部中央標準局負工消费合作社印裝 A7 B7 五、發明説明（Y) 基）—4 -甲基硫苄基氰化物，α — (4 —十二烷基苯基硬醢基氧亞胺基）一 4一甲基硫苄基氰化物，9一（4 —甲基苯基磺醢基氧亞胺基）_3，6—二甲氧基蓀* a — (4十二烷基苯基磺醢基氧亞胺基）_3，6 —二甲氧基蒹，9 一（4_ 甲基苯基磺醢基氧亞肢基）—1，6_二甲氧基葬，9— (4 一十二烷基苯基磺醢基氧亞胺基）一 1，6_二甲氧基荛， α - (2，4，6—參（甲基）苯基磺醢基氧亞胺基）—3，4 一二甲氧基苄基氰化物，α - (4 —硝基苯基磺醯基氧亞胺基）-3，4 —二甲氧基苄基氰化物，α — （2—丙基磺醯基氧亞胺基）一 4一甲基硫苄基氰化物，α — (4 —氛苯基磺醢基氧亞胺基）一4一甲基硫苄基氰化物，α — （3—三氟甲基苯基磺醢基氧一亞胺基）—4一甲基硫苄基氰化物，α —(4一硝基苯基磺醯基一氧亞胺基）—4—甲基硫苄基氰化物，α_ (甲基磺醢基氧亞胺基）一3，4一二硫甲基苄基氰化物，α — (4—甲基苯基磺醢基氧一亞胺基）一 3，4 一二硫甲基苄基氰化物，c(一（4 —甲基苯基磺醢基—氧亞胺基）一3—甲氧基一 4_甲基硫一苄基氰化物，α_ (甲基磺醢基氧亞胺基）—3—甲氧基一 4 —甲基硫-苄基氰化物，9— ( η—辛基磺醢基氧亞胺基）一 3，6—二甲氧基一蘋，9_ ( 4一十二烷基苯基磺醢基氧亞胺基）一3，6—二 (4 —羥基乙基硫）一蓀，3—(對一氰基一 1— 〔4_十二烷基苯基磺醢基氧亞胺基]—苄基）_5，7—二丁氧基一香豆素。 ~ 2 8 ~ 本紙張尺度適用中國國家揉準（CNS ) A4規格（210X29*7公釐） ----------^------IT------Φ, (請先閲讀背面之注意事項再填寫本頁) 五、發明説明（<) 物 A7 B7 本發明亦枏鼷於式I，la及lb化合物的異構形式的混合肟磺酸酯類（式I，la及lb)可Μ經由見述於文獻中的方法加Μ製備，例如經由將合適的游離肟類（式Π)與磺酸鹵化物類（式III)在一鹼的存在下，如三乙基胺*進行反應，或經由將肟鹽與一磺酸氛化物反應。這些方法揭示於，例如，ΕΡ— Α4 8 6 1 5。 R,-(CO)m-C(R2)=NOH + (CIS02)x-R3 R; 0 II -C- -C=N-〇-S〇i I ^ R, ---------------IT------.^ (請先閲讀背面之注意事項再填寫本頁) 經濟部中央橾準局負工消貧合作社印装 (II) (III) (I) 該反懕為有利地在惰性有櫬性溶劑中於一種三级胺的存在下進行。Rs and 1 are each independently hydrogen or (^ — Ci 2 alkyl, which is unsubstituted or via OH, Ci — C 4 alkoxy, Ci — Ci 2 alkylsulfonyl, phenylsulfonyl, (4 Monomethylphenyl) _sulfonyl and / or substituted by C! -Cs alkylfluorenyl and it may be interrupted by 10-, or R -26- This paper is based on Chinese standards ( CNS) A4 size (2 丨 OX297mm) I Binding II line (please read the precautions on the back before filling this page) The China Ministry of Economic Affairs, the Bureau of Quasi Bureau, Shellfisher Consumer Cooperative Du printed A7 _B7_ V. Description of the invention (^ * 1) S and R6 are phenyl, Ci-6 alkylfluorenyl, benzylfluorenyl, Ci-c6 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl, Zeolyl Sulfonyl, anthrylsulfonyl or phenanthrenesulfonyl, or R5 and R6, together with the nitrogen atom they bury, form a 5-, 6-, or 7-membered ring, which can be a 0- or Interrupted by a NR4—plus M; and R7 is a h 2 alkyl group that is unsubstituted or substituted via 0 Η and / or Ci-C4 alkoxy, and which may be additionally interrupted by —0— Is particularly advantageous Compound α- (methylsulfonamidooxyimino)-3,4-dimethoxy-benzyl cyanide, c (mono (4-dodecylphenylsulfamoyloxyimino) —3,4 —dimethoxybenzyl gaseous or α — (4-methyl-phenylsulfonyloxyimino) — 4-monothiomethylbenzyl cyanide, α — (2-propyl Sulfofluorenyloxyimino)-3,4-dimethoxybenzyl cyanide, α- (phenylsulfonyloxyimino)-3,4-dimethoxybenzyl cyanide, ( 4-methoxyphenylsulfonyloxyimino) -3,4-dimethoxybenzyl cyanide, α- (2,4,6--p- (isopropyl) -phenyl-sulfonamido Oxyimino)-3,4-dimethoxybenzyl cyanide, "-(η-octylsulfonyloxyimino)-3,4-dimethoxybenzyl cyanide, α- (4-monophenylphenylsulfonyloxyimino)-3.4-dimethoxybenzyl cyanide, a-(3-trifluoromethylphenylsulfonyloxyimino)-3, 4 —dimethoxybenzyl cyanide, α — (methylmonosulfonylaminoimine-27— This paper is based on Chinese standards (CNS > Α4 specification (210 × 297 mm) (please read the notes on the back before filling in this page) -Packing. Order printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives. A7 B7 V. Description of invention (Y) basis-4-A Thiothiobenzyl cyanide, α- (4-dodecylphenylhard fluorenyloxyimino) -4-methylthiobenzyl cyanide, 9- (4-methylphenylsulfonyloxy) Imino) _3,6-dimethoxyfluorene * a — (4-dodecylphenylsulfonyloxyimino) _3,6-dimethoxyfluorene, 9- (4-methylphenyl) Sulfofluorenyloxylimenyl) —1,6-dimethoxy, 9— (4-dodecylphenylsulfonyloxyimino) —1,6-dimethoxyfluorenyl, α -(2,4,6-Phenyl (methyl) phenylsulfonyloxyimino) -3,4-dimethoxybenzyl cyanide, α-(4-nitrophenylsulfonyloxy Imino) -3,4-dimethoxybenzyl cyanide, α- (2-propylsulfonyloxyimino) -4-methylthiobenzyl cyanide, α- (4- Phenylsulfonyloxyimino) -4-methylthiobenzyl cyanide, α- (3-trifluoromethylbenzene Sulfofluorenyloxyimino) —4-monomethylthiobenzyl cyanide, α— (4-nitronitrosulfonyloxyimino) —4-methylthiobenzyl cyanide, α_ (Methylsulfonyloxyimino) -3,4-dithiomethylbenzyl cyanide, α- (4-methylphenylsulfonyloxyimino) -3,4-disulfide Methyl benzyl cyanide, c (mono (4-methylphenylsulfonyl-oxyimino) -3-methoxy-4-methylsulfan-benzyl cyanide, α_ (methylsulfonium Oxyoxyimino) —3-methoxy-4-methylsulfanyl-benzyl cyanide, 9— (η-octylsulfonyloxyimino) —3,6-dimethoxy-methyl , 9_ (4-dodecylphenylsulfonyloxyimino)-3,6-di (4-hydroxyethylsulfuryl) -1,3- (p-cyano-1— [4_ten Dialkylphenylsulfonyloxyimino] -benzyl) -5,7-dibutoxy-coumarin. ~ 2 8 ~ This paper size is applicable to China National Standard (CNS) A4 (210X29 * 7mm) ---------- ^ ------ IT ------ Φ, (Please read the notes on the back before filling this page.) 5. Description of the invention (A7 B7) The present invention is also limited to the mixed oxime sulfonates of the compounds of formula I, la and lb (formula I, la and lb) can be prepared by the method described in the literature plus M, for example, by combining appropriate free oximes (formula II) and sulfonic acid halides (formula III) in the presence of a base, such as Triethylamine * is reacted, or by reacting an oxime salt with a monosulfonic acid sulphonate. These methods are disclosed in, for example, EP-A4 8 6 1 5. R,-(CO) mC (R2) = NOH + (CIS02) x-R3 R; 0 II -C- -C = N-〇-S〇i I ^ R, ---------- ----- IT ------. ^ (Please read the notes on the back before filling out this page) Printed by the Central Ministry of Economic Affairs, Central Bureau of Work, Anti-poverty Cooperatives (II) (III) (I) This The reaction is advantageously carried out in the presence of a tertiary amine in an inert solvent.

肟的钠鹽可K經由，例如，將相Μ之肟與酵酸納在DHF -29- 本紙浪尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）經濟部中央標準局貝工消費合作社印製 A7 B7_ 五、發明说明（vi) 中進行反應而得到。具有雜環芳香性 5-員環取代基之肟磺酸衍生物類的製備亦可經由合通的磺酸衍生物類，例如肟基丙二購的酯類或肟基氰基乙酸酷，之1，3—二極環.加成作用形成一合適的1 ，3—二極化合物，如一種腈氧化物。該類型的合成被描述於，例如， J. Perrocheau * R. Carre， Bull. Soc. Chim. Beige 1994 > 103， 9° 肟磺酸酯類可M syn (順式）及anti (反式）形式存在或為兩種構形異構物之混合物類。在本發明中，可K 使用兩種個別構形異構物類及任何兩種個別構形異構物類之混合物類。反應所需的式II之肟類可以習知方式進行類似地製備，例如，經由將含有反應性亞甲基基團類的化合物類，如苄基氰化物衍生物類或苯基乙酸衍生物類，與一種亞硝酸烷基酷，例如亞硝酸甲酯或亞硝酸異戊酯，及一種醇酸納，例如甲酵酸納。此類反應見述於，例如， in " The Systematic Identification of Organic Compounds"， John Wiley 及 Sons， New York» 1980* p.181，"The sodium salt of the oxime can be passed, for example, by mixing the phase oxime and the fermented acid in DHF -29- The standard of this paper applies the Chinese National Standard (CNS) A4 (210X 297 mm). Cooperative printed A7 B7_ V. Obtained by reaction in the description of the invention (vi). The preparation of oxime sulfonic acid derivatives with heterocyclic aromatic 5-membered ring substituents can also be carried out by combining sulfonic acid derivatives such as oxime propylene glycol esters or oxime cyanoacetic acid. 1,3-dipolar ring. Addition forms a suitable 1,3-dipolar compound, such as a nitrile oxide. This type of synthesis is described in, for example, J. Perrocheau * R. Carre, Bull. Soc. Chim. Beige 1994 > 103, 9 ° oxime sulfonates M syn (cis) and anti (trans) The form exists or is a mixture of two configurational isomers. In the present invention, two individual conformational isomers and a mixture of any two individual conformational isomers may be used. The oximes of formula II required for the reaction can be similarly prepared in a conventional manner, for example, by incorporating compounds containing reactive methylene groups such as benzyl cyanide derivatives or phenylacetic acid derivatives , And an alkyl nitrite, such as methyl nitrite or isoamyl nitrite, and a sodium alginate, such as sodium formate. Such reactions are described, for example, in " The Systematic Identification of Organic Compounds ", John Wiley and Sons, New York »1980 * p.181, "

Die Makromolekulare C h e m i e ^ ( MacroniolecularDie Makromolekulare C h e m i e ^ (Macroniolecular

Chemistry) ， 1967， 108， 170，或"Organic -30- 本纸張尺度逋用中國國家揉準（CNS > A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂線經濟部中央樣準局負工消费合作杜印装 A7 B7 五、發明説明（/|)Chemistry), 1967, 108, 170, or "Organic -30-" This paper size is based on the Chinese national standard (CNS > A4 size (210X297 mm) (Please read the precautions on the back before filling this page) Duanzhuang A7 B7, Work and Consumption Cooperation, Central Procurement Bureau, Ministry of Economic Affairs

Synthesis" ， 1 9 7 9 ; 59， 95 .肟類之獲得可經由一相對應的羰基化合物或亞硫醢羰基化合物與羥基胺進行反應。進一步的可能性為羥基_芳香性化合物類的硝化作用。磺酸鹵化物類（式 III)的製備對於姻於此技藝者而言為熟習的且見述於，例如，慣用的化學教科書。肟磺酸酯類可被用於作為光一可活化的硬化劑類供酸-可熟化的樹脂類之光-可活化的硬化劑類。合適的酸一可熟化的樹脂類為所有熟化可以酸觸媒類加速的樹脂類，如胺基塑料類或酚性可溶酚醛樹脂類。這些樹脂類特別可為三聚氰胺，尿素，環氧化物，酚性，丙烯性，聚酯及酵酸樹脂類，但特別是丙烯性，聚酯或酵酸樹脂類與一種三聚氰胺樹脂的混合物。亦被包括的是經改質的表面一被覆樹脂類，如丙烯性-改霣性聚酯及醇酸樹脂類。可為丙烯性，聚酯及醇酸樹脂類所表示之個別種類的樹脂類實施例見述於 * 例如，Wagner > Sarx/ Lackkuns tharz e ( Munich > 1371)，第86頁至第123頁及第2 2 9頁至第238頁，或見述於 Ullmann/1 Encyclopadie der t e c hn . Chemie，4th Edition > Volume 1 5 ( 1 9 78)，第 6 1 3頁至第 6 2 8頁，或 Ullmann' s Encyclopedia of Industrial Chemistry * Verlag Chemie， 1991 * Vol.18 > 360ff.， Vol.A19 * 本紙張尺度逋用中國國家揉準（CNS > A4規格（210X 297公釐） « » ---------.1^------tr------A (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印裝 A7 B7_ 五、發明説明（) 表面被覆偏好包括一種胺基樹脂。其實施例為醚化的或非一醚化的三聚氰胺，尿素，胍或二縮脲樹脂類。在表面被覆的热化作用中酸催化作用為特別重要的，該表面被覆包括***化的胺基樹脂類，如甲基化的或丁基化的三聚氰胺榭脂類（N—甲氧基甲基一或N — 丁氧基甲基一三聚氰胺）或甲基化的/ 丁基化的甘脲類（glycolurils)。其他樹脂组成物類的實例為多官能性醇類或羥基一基團-內含性丙烯性及聚酯樹脂類的混合物類，或具有多官能性二氫丙基衍生物類之部份地被水解的聚乙烯基乙酸酯或聚乙烯基酵，如3，4一二氫一喃_2—羧酸之衍生物類。如前文所提及者，例如聚矽氧烷類，亦可使用酸催化作用進行交叉聯结。其他適合製備表面被覆物的陽離子性可聚合的材料為伸乙基性不飽和的化合物類，其可經由一陽離子性機種成為可聚合的，例如經由如乙烯基醚類，例如甲基乙烯基醚，異丁基乙烯基醚，三羥基甲基丙烷三乙烯基醚，亞乙基乙二醇二乙烯基醚，環狀乙烯基醚類，例如3，4 —二氫一 2_甲醢基一 2H_吡喃（二元性丙烯醛）或2-羥基甲基一 3，4 -二氫一 2H —吡喃之 3，4一二氫—2H-K 喃一 2-浚酸酯；乙烯基酯類，如乙酸乙烯酯及應脂酸乙烯酯，單 --及二一烯類，如α —甲基苯乙烯，N—乙烯基砒咯酮或 _Ν_乙稀基—卡哩。 -32- 本纸張尺度適用中國國家揉率（CNS ) Α4规格（210X297公釐） ---------^丨^------?τ------# (請先閱讀背面之注意事項再填寫本頁) 經濟部中央樣準局貝工消費合作社印装 A7 B7 五、發明説明（f ) 為了一些目的，使用含可聚合的不飽和的基圈類之單體性或寡通性組成分之樹脂混合物類。此種表面被覆物類可以使用式I，la及lb之化合物進行熟化。在此過程中，可 Μ額外地使用a)自由基聚合作用起動劑類或b)光起動劑類。前者起動不飽和基ffl在熱處理時的聚合作用，後者則在（JV輻射時有同樣的效果。額外的光起動劑類的實施例為，例如；自由基光起動劑類，如來自二苯嗣類，苯乙酮衍生物類*如羥基環烷基苯基颳，二烷氧基苯乙嗣，α -羥基一或cx -胺基一苯乙酮，4 -芳醢基一1，3 -二氧伍環類，安息香（benzoin) 烷基醚類及苯偶醢（benzil)醛類，單醢基膦氧化物類，雙醢基膦氧化物類或titanocenes。特別合適的額外的光起動劑類的實施例為：1 一（4_十二烷基苄醢基）_1一羥基 -1—甲基—乙烷，1一（4 一異丙基苄醢基）一1 一羥基一1 一甲基一乙烷，1一苄醢基一 1—羥基一 1 一甲基_乙烷，1 一〔4— (2 —羥基乙氧基）一苄醢基-〕一 1 一羥基一1 一甲基一乙烷，1_ [4—(羥基丙烯基氧乙氧基）一苄醢基] 一 1 一羥基一 1 一甲基一乙烷，二苯基嗣，苯基—1 一羥基— 環己基酮，（4_嗎啉基苄醢基）一1一苄基—1一二甲基胺基一丙烷，1— (3，4 一二甲氧基苯基）一2 —苄基一 2—二甲基胺基一丁一 1-嗣，（4 —甲基硫苄醢基）一1一甲基一 1-嗎啉基一乙烷，苯偶醢（benzil)二甲基醛，雙（環戊 -33- 本紙朱尺度逍用中國國家棣準（CNS ) Α4说格（210X 297公釐） ---------^------ΐτ------^ {諳先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消费合作社印装 A7 _B7__ 五、發明説明&ί>) 二烯基）一雙（2，6 —二氟一 3—吡咯基一苯基）钛，三甲基苄醢基二苯基膦氣化物，雙（2，6 -二甲氧基-苄醯基 )-(2，4，4一三甲基一戊基）一滕氧化物，雙（2，4, 6—三甲基苄醢基）一 2· 4—二戊基氧苯基一膦氧化物或雙 (2，4，6_三甲基苄醢基）苯基一膦氧化物。進一步合適的額外光起動劑類被發現於US專利4 9 5 058 1中，第20播，第 35行至第21播，第35行。其它的實施例為三鹵甲基三嗪衍生物類或六芳基雙眯唑基化合物類。額外的光起動劑類之進一步實施例為，例如，陽離子性光起動劑類，如過氧化物化合物類，例如苄醢基過氧化物（其他合適的過氧化物類見述於US專利4 950 581，第 19禰，第 17— 25行），芳香性磺銪或碘銪鹽類，如可於 US專利4 9 5 0 5 8 1，第18檷，第60行至第19禰，第10 行發現者，或環戊二烯基一芳烴一鐵（II)錯合鹽類*例如（η6 _異丙基苯）—（5—環戊二烯基）一鐵（II)六氟磷酸。表面被覆物類可為表面一被覆樹脂於有欐性溶劑或於水中形成的溶液類或分散液類，但是他們亦可不含溶劑。特別有利的是具有低份量溶劑之表面被覆物類，即所謂的 "高固體表面被覆物類"，及粉末被覆组成物類。表面被覆物類可為澄清塗漆，其例如用於汽車工業作為多層被覆本紙張尺度適用中國國家標準（CNS > Α4规格（210X297公釐） ---------Κ裝------訂------镍 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標率局負工消费合作社印製 Α7 Β7 五、發明説明（>1) 的最後塗漆。他m1@含色素’其可為無櫬性或有機性色素，及金靥粉末以供金靨效果的完工塗漆。表面被覆物類亦可包含相當少童之慣用於表面-被覆技術的特別添加物類’例如流動性改菩劑類，觸變劑類* 光穩定劑類，抗氧化劑類或敏慼劑類。 uv吸收劑類，例如羥基苯基苯並****羥基苯基苯並酚，乙二醢二胺或羥基苯基- S —三嗪類型的化合物。這些化合物類可以個別或K混合物類的形式加Μ使用，可與或不與立髖性障礙之胺類（HALS)聪用。 UV吸收劑類及光安定劑類的實施例類為： 1 . 2 - ( 2 ' —羥基苯基）苯在***類，例如2 — ( 2' — 羥基-5' _甲基苯基）苯並***，2— （3' ，5' -二— 第三一丁基一 2' —羥基苯基）苯並***，2— (5^ _第三 _ 丁基—2'—羥基苯基）苯並***，2_ (2' -羥基一 5 ’ -(1，1，3，3 —四甲基丁基）苯基）苯並***，2- (3' ，5' —二一第三—丁基-2' —羥基苯基）一 5-氛苯並***，2 — （ 3' _第三一丁基一 2, —羥基~ δ, —甲基苯基）~5—氛苯並***，2— （3，一第二一丁基一 5' 一第三一丁基—2，一羥基一苯基）苯並***，2- （2' - -35- 本纸張尺度適用中國國家揉率（CNS > Α4规格（210X297公釐） ----------裝-- (請先閲讀背面之注$項再填寫本頁) 訂線經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明羥基—4' 一辛氧基苯基）苯並***，2_ (3< ，5'—二一第三—戊基—2' -羥基苯基）苯並***，2_ (3' ，5 '一雙（α，α —二甲基苄基）一2'—羥基苯基）苯並三唑，由2- (3'-第三-丁基-2^ -羥基一5^ -2-辛基氧羰基乙基）苯基）— 5-氯苯並***，2 — （ 3' —第三 —丁基一 5/ — 〔2— (2 —乙基己基氧）羰基乙基〕一 2' —羥基苯基）_5—氯苯並***，2 — （3' —第三一丁基一 2'—羥基一5' — (2—甲氧基羰基乙基）苯基）一5—氛苯並***，2— （3' —第三一丁基一 2'—羥基—5' — (2 —甲氧基羰基乙基）苯基）笨並***，2— (3'—第三一丁基—2' -羥基_5' — （2 —辛基氧羰基乙基）苯基）苯並***，2- (3' —第三一丁基一 5' — 〔2— （2 —乙基己基氧）羰基乙基]—V —羥基苯基）苯並***，2— (3' —十二烷基一2' —羥基_5' —甲基苯基）苯並***，及2 —(3^ —第三一丁基—2'—羥基—5' _ (2—異辛基氧羰基乙基#$***所組成的混合物，2，2'-亞甲基雙 C 4 - (1，1，3，3—四甲基丁基）一6 —苯並***一2 —基酚〕；2— 〔3' —第三一丁基一5' - (2—甲氧基羰基乙基）―2'—羥基苯基〕家並***與聚伸乙基乙二醇3(30之轉酯反應產物；〔R-CH2 CH2 — C00(CH2)3〕2 ，其中R=3'—第三-丁基—4 ' 一羥基-5' - 2H —苯並*** _ 2 -基苯基。 -36- 本紙張尺度適用中國國家揉準（CNS ) A4規格（210X29*7公釐） ---------1^------IT------# (請先閲讀背面之注意事項再填寫本頁) A7 B7Synthesis ", 179 9; 59, 95. The oxime can be obtained by reacting a carbonyl compound or a thionyl carbonyl compound with a hydroxylamine. A further possibility is the nitration of hydroxy-aromatic compounds. The preparation of sulfonic acid halides (formula III) is familiar to those skilled in the art and is described in, for example, conventional chemistry textbooks. The oxime sulfonates can be used as photo-activatable hardeners for acid-curable resins, photo-activatable hardeners. Suitable acid-curable resins are all resins whose curing can be accelerated by acid catalysts, such as amine plastics or phenolic soluble phenolic resins. These resins may be, in particular, melamine, urea, epoxide, phenolic, acrylic, polyester and fermented resins, but especially a mixture of acrylic, polyester or fermented resins with a melamine resin. Also included are modified surface-coating resins, such as acrylic-modified polyesters and alkyd resins. Examples of individual resins that can be acrylic, polyester and alkyd resins are described in * For example, Wagner > Sarx / Lackkuns tharz e (Munich > 1371), pages 86 to 123 And pages 2 29 to 238, or see Ullmann / 1 Encyclopadie der tec hn. Chemie, 4th Edition > Volume 1 5 (1 9 78), pages 6 1 3 to 6 2 8 Or Ullmann's Encyclopedia of Industrial Chemistry * Verlag Chemie, 1991 * Vol. 18 > 360ff., Vol. A19 * This paper is based on the Chinese national standard (CNS > A4 size (210X 297 mm) «»- --------. 1 ^ ------ tr ------ A (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7_ 5. Description of the invention () Surface coating preferences include an amine-based resin. Examples are etherified or non-monoetherified melamine, urea, guanidine, or biuret resins. Acid catalysis during the heating of the surface coating The effect is particularly important. The surface coating includes etherified amine resins, such as methylated or butylated trimer. Cyanoamines (N-methoxymethyl-mono or N-butoxymethyl-melamine) or methylated / butylated glycolurils. Examples of other resin compositions are Polyfunctional alcohols or hydroxyl-group-containing acrylic and polyester resin mixtures, or partially hydrolyzed polyvinyl acetates with polyfunctional dihydropropyl derivatives Or polyethylene-based enzymes, such as derivatives of 3,4-dihydro-mono-2-carboxylic acid. As mentioned above, such as polysiloxanes, acid catalysis can also be used for cross-linking. Other cationic polymerizable materials suitable for preparing surface coatings are ethylenically unsaturated compounds, which can be made polymerizable via a cationic machine, such as via vinyl ethers such as methyl vinyl ether , Isobutyl vinyl ether, trihydroxymethylpropane trivinyl ether, ethylene glycol divinyl ether, cyclic vinyl ethers, such as 3,4-dihydro-1, 2-methylamino-1 2H_pyran (binary acrolein) or 2-hydroxymethyl-3,4-dihydro-2H Pyranyl 3,4-dihydro-2H-K sulfan-2-ester; vinyl esters, such as vinyl acetate and vinyl acetate, mono- and dienes, such as α-methyl Styrene, N-vinylpyrrolidone or _N_ethenyl-carbile. -32- This paper size applies to China National Kneading Rate (CNS) Α4 size (210X297 mm) --------- ^ 丨 ^ ------? Τ ------ # ( Please read the notes on the back before filling in this page.) Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Shellfish Consumer Cooperative, printed A7, B7. 5. Description of the invention (f) For some purposes, use a list containing polymerizable unsaturated base rings. Physical or oligomeric resin mixtures. Such surface coatings can be cured using compounds of formula I, la and lb. In this process, a) radical polymerization initiators or b) light initiators may be additionally used. The former starts the polymerization of unsaturated group ffl during heat treatment, while the latter has the same effect when (JV radiation). Examples of additional photostarters are, for example; radical photostarters, such as from diphenylhydrazone Class, acetophenone derivatives * such as hydroxycycloalkylphenyl scrape, dialkoxyacetophenone, α-hydroxyl or cx-aminomonoacetophenone, 4-arylfluorenyl-1,3- Dioxane rings, benzoin alkyl ethers and benzil aldehydes, monofluorenylphosphine oxides, bisfluorenylphosphine oxides or titanocenes. Particularly suitable additional light starters Examples of classes are: 1- (4-dodecylbenzylfluorenyl) _1-hydroxy-1 -methyl-ethane, 1- (4-isopropylbenzylfluorenyl) -1 1-hydroxyl 1 1 Methyl-ethane, 1-benzylfluorenyl-1-hydroxy-1, 1methyl-ethane, 1- [4- (2-hydroxyethoxy) -benzylfluorenyl-]-1-hydroxyl-1 1 Methyl-ethane, 1_ [4- (hydroxypropenyloxyethoxy) -benzylfluorenyl]-1-hydroxy-1 1-methyl-ethane, diphenylfluorene, phenyl-1-hydroxyl-cyclohexyl ketone (4_morpholinylbenzylfluorenyl) -1,1-benzyl-1-dimethylamino-propane, 1- (3,4-dimethoxyphenyl), 2-benzyl, 2-di Methylamino-butane-l-fluorenyl, (4-methylthiobenzyl), 1-methyl-l-morpholinyl-ethane, benzil dimethylaldehyde, bis (cyclic E-33- This paper is a Chinese version of the Chinese standard (CNS) Α4 grid (210X 297 mm) --------- ^ ------ ΐτ ------ ^ {谙 Read the precautions on the back before filling this page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, printed A7 _B7__ 5. Description of the invention & ί >) Dienyl) One pair (2, 6 —Difluoro-1 3 — Pyrrolyl monophenyl) titanium, trimethylbenzylfluorenyl diphenylphosphine vapor, bis (2,6-dimethoxy-benzylfluorenyl)-(2,4,4-trimethylmonopentyl) ) One tenth oxide, bis (2,4,6-trimethylbenzylfluorenyl) -2.4-dipentyloxyphenyl-phosphine oxide or bis (2,4,6-trimethylbenzylfluorene) Group) phenyl monophosphine oxide. Further suitable additional light starters are found in US Pat. No. 4,995,058 1, broadcast 20, 35 to 21, 35. Other examples are trihalomethyltriazine derivatives or hexaarylbisoxazolyl compounds. Further examples of additional light starters are, for example, cationic light starters, such as peroxide compounds, such as benzamidine peroxide (other suitable peroxides are described in US Patent 4,950). 581, line 19 祢, lines 17-25), aromatic sulfonium or iodonium salts, such as those available in US Patent 4 9 5 0 5 8 1, line 18 檷, lines 60 to 19 祢, line 10 Line finders, or cyclopentadienyl-arene-iron (II) complex salts * such as (η6- cumene)-(5-cyclopentadienyl) -iron (II) hexafluorophosphate. The surface coatings may be solutions or dispersions in which a surface-coated resin is formed in a harsh solvent or in water, but they may be solvent-free. Particularly advantageous are surface coatings having a low amount of solvent, so-called " high solid surface coatings ", and powder coating compositions. Surface coatings can be clarified paints, which are used in the automotive industry as multi-layer coatings. The paper size is applicable to Chinese national standards (CNS > Α4 specification (210X297 mm) --------- Κ 装- ---- Order ------ Nickel (Please read the notes on the back before filling out this page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives A7 Β7 V. The end of the description of the invention (> 1) Painting. He m1 @ containing pigments, which can be non-natural or organic pigments, and gold tincture powder for the finished painting of gold tincture effect. Surface coatings can also contain quite a few children's customary surface-coating Special additives of the technology, such as fluid modifiers, thixotropic agents * light stabilizers, antioxidants or sensitizers. UV absorbers, such as hydroxyphenylbenzotriazole * hydroxybenzene Benzophenol, ethylenediamine or hydroxyphenyl-S-triazine type compounds. These compounds can be used individually or in the form of K mixtures, with or without amines with orthopedic disorders (HALS) for Satoshi. Examples of UV absorbers and light stabilizers are: 1.2-(2 '-hydroxyl Phenyl) benzene in triazoles, such as 2- (2'-hydroxy-5'_methylphenyl) benzotriazole, 2- (3 ', 5'-di-tertiary-butyl-2' —Hydroxyphenyl) benzotriazole, 2- (5 ^ _third_butyl-2′-hydroxyphenyl) benzotriazole, 2_ (2′-hydroxy-5 ′-(1,1,3 , 3-tetramethylbutyl) phenyl) benzotriazole, 2- (3 ', 5'-di-third-butyl-2'-hydroxyphenyl) -5-nitrobenzotriazole, 2 — (3 ′ _ third monobutyl-2, —hydroxy ~ δ, —methylphenyl) ~ 5 — benzobenzotriazole, 2 — (3, a second butyl-5 '-first Tris-butyl-2, mono-hydroxy-phenyl) benzotriazole, 2- (2 '--35- This paper size applies to China's national kneading rate (CNS > A4 size (210X297 mm) --- ------- Packing-(Please read the note on the back before filling in this page) Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, printed A7 B7 V. Description of the invention Hydroxy-4'-octyloxy Phenyl) benzotriazole, 2_ (3 <, 5'-di-third-pentyl-2'-hydroxyphenyl) benzotriazole, 2_ (3 ', 5'-bis (α, α- two Methylbenzyl) -2'-hydroxyphenyl) benzotriazole, consisting of 2- (3'-third-butyl-2 ^ -hydroxy-5 ^ -2-octyloxycarbonylethyl) phenyl ) — 5-chlorobenzotriazole, 2 — (3′-third-butyl-5 / — [2- (2-ethylhexyloxy) carbonylethyl] —2′-hydroxyphenyl) _5— Chlorobenzotriazole, 2- (3'-tertiary-butyl- 2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) 5- 5-benzobenzotriazole, 2- (3'-Third-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) Benzotriazole, 2- (3'-Third-butyl-2' -Hydroxy_5 '— (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3 ′ —third-butyl-5 ′ — [2— (2-ethylhexyloxy) Carbonylethyl] -V-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, and 2- (3 ^ —Third-butyl-2'-hydroxy-5'_ (2-isooctyloxycarbonylethyl # $ triazole mixture, 2,2'-methylenebisC 4-(1, 1,3,3-tetramethylbutyl) 6-benzotriazol-2-ylphenol]; 2- [3'-third-butyl-5 '-(2-methoxycarbonylethyl) -2'-hydroxyphenyl] Product of transesterification reaction of azole with polyethylene glycol 3 (30; [R-CH2 CH2 — C00 (CH2) 3] 2, where R = 3′-third-butyl-4′-hydroxy-5 '-2H —benzotriazol-2-ylphenyl. -36- This paper size is applicable to China National Standard (CNS) A4 (210X29 * 7mm) --------- 1 ^ ------ IT ------ # (Please (Please read the notes on the back before filling out this page) A7 B7

()V 五、發明説明 2.2 -羥基苯並酚類，例如4 一羥基，4 —甲氧基，4-辛氧基，4 —癸基氧，4 —十二烷基氧，4 —苄基氧，4，2' ，4'—三羥基及2' 一羥基_4，4' 一二甲氧基衍生物類 3.未經取代的或經取代的之苯甲酸酯類，例如柳酸4 -第三一丁基-苯基酯，柳酸苯基酯，彻酸辛基苯基酯，二苄醢基間苯二酚，雙（4 一第三—丁基苄醯基）間苯二酚，苄醢基間苯二酚，3，5—二一第三一丁基一4 —羥基苯甲酸2，4 —二—第三一丁基苯基酯，3，5 -二一第三-丁基 _4 —羥基苯甲酸十六烷基酯，3，5 —二一第三一丁基_4 一羥基苯甲酸十八烷基酯，3，5 —二一第三一丁基一 4一羥基苯甲酸2—甲基一4，6 —二一第三一丁基苯基酯。 4凋妹酸酯類，例如α —氰基* /3 —二苯基丙烯酸乙基及異辛基酯，α—碳甲氧基苯基丙烯酸甲基酯，α_ 氰基一点一甲基—ρ—甲氧基苯基丙烯酸甲基及丁基酯，α 一碳甲氧基一 Ρ _甲氧基苯基丙烯酸甲基酯及Ν — （ yS —碳甲氧基—氰基乙烯基3—2 —甲基吲哚啉。 5.立體阻礙性胺類，例如雙（2，2，6，6 -四甲基哌啶基）癸二酸，雙（2，2，6，6 —四甲基锨啶基）丁二酸，雙（1，2，2，6，6 —五甲基呢啶基）癸二酸，雙（1， -37- 本紙张尺度適用中國國家標準（CNS ) A4規格（210X297公釐） --------1^------1T------^ (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製經濟部中夬標準局員工消費合作社印製 Α7 Β7 五、發明説明（）产，2，6，6_五甲基呢陡基）η— 丁基一 3，5 —二一第三— 丁基一 4 一羥基苄基丙二酸，1 一羥基乙基一 2，2，6，6 — 四甲基一 4 一羥基咪啶及丁二酸之縮合反應的產物，Ν，Ν' 一雙（2，2，6，6 —四甲基一 4 一哌啶基）六亞甲基二胺及 4一第三一辛基胺基—2，6—二氛一1，3，5—s—三曝之縮合反懕的產物，參（2，2，6，6—四甲基一 4一哌啶基）腈醢基三乙酸，肆（2，2，6，6—四甲基一 4 一哌啶基）1，2 *3，4一丁烷四酸，1，广—(1，2—乙烷二基）雙一（3 ，3,5,5 —四甲基哌嗪_) ，4 -苄醢基一 2，2，6* 6—四甲基哌啶，4 一硬脂醢基氧一 2，2，6，6_四甲基呢啶，雙（ 1，2，2，6，6—五甲基呢陡基）2—Π-丁基一2— (2—經基一 3，5 -二一第三-丁基苄基）丙二酸，3-η—辛基一 7 ，7，9，9 -四甲基_1，3，8 -三氮雜螺〔4.5]癸烷一 2 ，4 一二酮，雙（1—辛基氧一 2，2，6，6—四甲基哌啶基 )癸二酸，雙（1一辛基氧一 2，2，6，6—四甲基锨啶基）丁二酸，Ν，Ν' —雙（2，2，6，6 —四甲基一 4 一锨啶基六亞甲基二胺與4 —嗎啉基一 2，6 —二氯—1，3，5—三嗪之締合反應的產物，2—氣—4，6 —二（4 一 η— 丁基胺基一 2 ，2，6，6-四甲基锨啶基）1，3，5—三嗪與1，2—雙（ 3—胺基丙基胺基）乙烷之縮合反應的產物，2 —氛一 4，6 一二（4— η—丁基肢基一 1，2，2，6，6-五甲基哌啶基） —1，3，5-三嗪與1，2—雙（3_胺基丙基胺基）乙烷之縮合反應的產物，8 —乙醢基一3—十二烷基一 7，7，9，9 -3 8 - 本紙張尺度逋用中國國家橾準（CNS ) Α4規格（210Χ297公釐） ---------1赛------1Τ------ (請先Μ讀背面之注$項再填寫本頁) 經濟部中央標隼局員工消費合作社印装 A7 B7 五、發明説明（j/) 一四一甲基一1，3，8-三氮雜螺〔4.5]癸烷一2，4 —二嗣，3—十二烷基一 1 一（2，2，6，6 —四甲基—4—哌啶基 )砒咯啶一2，5- 二酮，3—十二烷基—1一（1，2，2，6 * 6 —五甲基一4 —呢陡基）此塔陡―2，5 —二酮。 6.乙二醢二胺類，例如4，4'-二辛基氧乙二醢替苯胺，2，2' —二乙氧基乙二醢替苯胺，2，2'-二辛基氧 —5，5_二一第三—丁基乙二醢替苯胺，2，2'-二十二烷基氧-5，5' —二一第三一丁基乙二醢替苯胺，一乙氧基一2' —乙基乙二醢替苯胺，Ν，Ν' —雙（3—二甲基胺基丙基）乙二酿二胺，2 —乙氧基—5 —第三—丁基一 2' - 乙基乙二醢替苯胺及其與2—乙氧基—2'—乙基一 5，4' —二一第三一丁基乙二醯替苯胺的混合物，及〇 -及Ρ—甲氧基-及〇 —及Ρ—乙氧基一二經取代之乙二醢替苯胺類之混合物類。 7.2- (2 —羥基苯基）-1，3，5—三嗪類，例如2， 4，6 —參（2_羥基—4 —辛基氧苯基）-1，3，5—三嗪， 2 - (2 —羥基一 4 —辛基氧苯基）_4，6—雙（2，4 —二甲基苯基）一 .1，3，5—二嗓，2— (2，4 —二控基苯基）— 4，6_ 雙（2，4 -二甲基苯基）一1，3，5 —三嗪，2，4 一雙（2 —羥基一 4 一丙基氧苯基）—6— （2，4_二甲基苯基）一1，3，5—三嗪，2— （2 —羥基—4 一乙烯基氧苯基 -39- 本紙張尺度遑用中國國家標準（CNS ) Α4洗格（210X297公釐）裝訂線 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 A7 B7 五、發明説明（%) )_4，6 —雙（4 一甲基苯基）一 1，3，5 -三嗪，2 — （2 一羥基一4 -十二烷基氧苯基）一 4，6 —雙（2，4 —二甲基苯基）一1*3，5-三嗪，2_ 〔2—羥基一 4一（2—羥基一 3-丁基氧丙基氧）苯基〕一 4，6—雙（2，4一二甲基苯基 )—1，3，5 —三嚷，2— 〔2 —控基一 4 一（2— 控基—3 — 辛基氧一丙基氧）苯基]一 4，6 —雙（2，4 -二甲基苯基 )-1，3，5—三嗪及2— 〔4 一十二烷基/十三烷碁氧（2 一羥基丙基）氧一 2 —羥基苯基]一 4，6—雙（2，4一二甲基—苯基）1，3，5-三嗪。 8·亞磷酸酯類及亞膦酸酯類，例如亞磷酸三苯基酯，亞磷酸烷基二苯基鹿，亞«酸二烷基苯基酷，亞磷酸參一 (壬基苯基）酯*亞磷酸三月桂醢基醱，亞磷酸三（十八烷基）酯，二亞磷酸第四戊四酵基二異脂醢基酯，亞磷酸參（2，4_二一第三一丁基苯基）酯，二亞磷酸二異癸基 —第四戊四酵基酯，二亞磷酸第四戊四醇基雙（2.4-二一第三一丁基苯基）酯，二亞磷酸第四戊四酵基雙（2，4 _ 二一第三一丁基一 4一甲基苯基）酯，二亞磷酸二異癸基氧 —第四戊四酵基酯，二亞磷酸第四戊四酵基雙（2，4 —二一第三一丁基一 6—甲基一苯基）酯*二亞璘酸第四戊四酵基雙（2，4，6—三一第三一丁基苯基）酯，三亞磷酸山梨酵參硬脂醢基酯，肆-(2，4 一二一第三一丁基苯基）-4 ，4' 一聯次苯基二亞磷酸酯，6 —異辛基氧一2，4，8 ， -40- 本紙張尺度逋用中國國家橾率（CNS ) Α4说格（210Χ297公釐） ---------------、訂------^ (請先Μ讀背面之注意事項再填寫本頁) 經濟部中央橾準局貝工消費合作社印裂 A7 £7_ 五、發明説明”]) 10—四一第三一丁基一12H-二苄基〔d，g〕一 1，3，2 -二聘基 phosphocine，6 —氣一2，4，8’ 10 —四—第二一丁基一 12 -甲基一二苄基〔d.g] -1，3，2—二聘基 phosphocine，亞磷酸雙（2，4 —二一第三一丁基-6—甲基苯基）甲基酯，及亞磷酸雙（2，4一二一第三一丁基一6 一甲基苯基）乙酯。此種光穩定劑類亦可被加入，例如，一鄰近的表面一被覆層，自該層光穩定劑類逐漸擴散進入待保護之烤漆層。鄰近的表面一被覆層可為在烤漆層下的原始層或在該烤漆層上之完成性塗漆。亦有可能在樹脂中加入，例如，光敏感劑類，其轉移或增加光譜敏感性，使得輻射期間可Μ縮短及/或使用其他的光源。光敏感劑類的實施例為芳香性酮類或芳香性醛類（見述於，例如， US專利 4 017 652) ， 3—醢基- 香豆素類（見述於，例如， US專利4 366 228)， 3 — (芳醢基亞甲基）-唾唑啉類•硫黃_類，被縮合的芳香性化合物類，如二萘嵌苯（perylene)，芳香性胺類（見述於，例如， US專利4 069 954)或陽離子性及鹼性著色劑類（見述於，例如， US專利4 Q26 705)，例如伊紅，繞丹寧（rhodanine)及赤薛紅（erythrosine)著色劑類. -4 1- 本紙張尺度適用中國國家橾準（CNS )八4规格（210X297公漦） --------TP#------IT------^ (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消费合作社印製 A7 B7 五、發明説明其他慣用的添加劑類一視意欲的目的-為光學性明亮劑類，填充劑類，色素類，著色劑類，濕濶劑類或流動性改良劑類。為了熟化厚的且攙雜色素的被覆物類，加入微玻璃珠或粉狀玻璃珠，其見述於 US-A-5 013 768，為合適的。額外的光起動劑類或添加劑類之其他實施例已在前文敘述 Ο 肟磺酸酯類亦可被用於，例如，雜混性（hybrid)糸統中。這些系統基於被兩種相異的反應機制所熟化的配方。實施例為包括能夠經歷酸-催化***叉聯结反應或聚合作用反應的成份，且亦包括可經由第二種機制交叉聯结的進一步成份的系統。第二種機制的實施例，例如，為自由基完全熟化，氧化***叉聯结或濕氣-起動式交叉聯结。第二種熟化機制可單纯地由加熱起始*若有需要，使用一合適的觸媒，或亦可經由使用第二種光起動劑的光。根據本發明，可光活化的組成物類，除了成份 c) Μ 外，可進一步包括光起動劑類，敏感劑類及/或添加物類，或式I，la或lb之化合物類可與進一步之光起動劑類，敏感劑類及/或添加劑類聯用。 -42- 本紙張尺度適用中國國家標準（CNS ) ( 210X297公釐） I I — — — —— I I I I I I n ^ 1 線 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印装 A7 B7_ 五、發明説明（1) 若該組成物包括一自由可交叉聯结的成份，該熟化方法，特別是針對攙雜色素的組成物類（例如使用二氧化钛 )，亦可藉助於加入在熱條件下為自由基一形成性的成份，如一種叠氮化合物，例如2，2—叠氮雙（4 —甲氧基一 2 ，4 —二甲基戊腈），三氮烯（triazene)，二叠氮亞硫酸物，五氮二烯（pentazadiene)或一種過氧化合物*如* 例如，過氧化氫或過氧碳酸物，例如第三- 丁基過氧化氫，其見述於，例如，EP-A245639。加入堪原氧化性起動劑類，如鈷鹽類，使得熟化可藉助於來自空氣中的氧進行氧化***叉聯结。表面被覆物可經由在本技藝中一種慣用的方法進行施用，例如經由噴灑，塗刷或浸入。當使用合適的表面被覆物類時*電子式施用，例如經由電浸被覆，亦為可能的。在乾揉之後，表面被覆物薄層被蟠射。若有需要，表面被覆物薄層經由熱處理而完全熟化。式I， la及lb之化合物類亦可被用於熟化自複合物製成的摸製物類。一個複合物包括一種自行一支持性基質材料，例如一種玻璃繼維纗物，其Μ光热化配方包埋。姐抗物質系統可Κ經由逐像輻射包括式I， la或lb之 -43- 本紙張尺度適用中國國家揉準（CNS } A4规格（210X297公釐） ----------Γ裝------訂------線 (請先閲锖背面之注意事項再填寫本頁) 經濟部中央操準局貝工消費合作社印製 A7 B7__ 五、發明説明（(/：〇) 化合物類的系統，接著使用顯影步驟。如已提及者，式 1 ’ la及lb之化合物類可被用於作為在一光阻物質中的光敏感性酸提供者，特別是供波長超過390微奄米的輻射。本發明據此亦相關於一種光阻物霣K供波長超過390微 €米的輻射，其基於肟磺酸酯類作為感光性酸提供者，該光阻物質，包括式I， la或lb之化合物作為肟磺酸酯。介於被輻射的及非被輻射的部份之間的溶解性的不同之發生成因為阻抗材料在該阻抗物質的輻射時或之後之酸一催化性反應可為兩種型態，由於這種结果，進一步的組成分出現在阻抗物質中。若本發明之組成物類包括在輻射後增進組成物在顯影劑中的溶解性的成份，該阻抗物質為正性。若，另一方面，這些成份可降低在輻射後降低組成物在顯影劑中的溶解性的成份，該阻抗物質為負性。本發明據此亦相關於一種負性光阻物質及相關於一種正性光阻物質。式I，la及lb的肟磺酸酯類亦可被用於化學性增幅的阻抗物。一化學性擴大效果的光阻物質被瞭解為一種阻抗物質組成物的感光性成份，在被輻射之後，僅提供需要催化該狙抗物質之至少一種酸一敏感性成份之化學反應的酸份 -4 4 - 本紙張尺度適用中國國家揉準（CNS ) A4規格（210X297公釐） ---------装------1T------^ (請先閲讀背面之注意事項再填寫本頁) 、經濟部中央樣隼局貝工消費合作社印製 A7 B7 五、發明説明（彳I) 量，由此開始發展出介於被輻射的及非被輻射的區域之間的最終不同溶解性。本發明據此亦相關於一種化學性擴大效果的光阻物質. 該種阻抗物對於長波長輻射，特別是超過3 9 0微牽米之輻射，表現一種明顯的石版印刷敏感性。根據本發明的光阻物質類具有優良的石版印刷特性，特別是高度的敏感性，且其亦具有與近UV範圍的輻射反應的優點，近UV範圍的輻射基本上由技術觀點而言較易於使用。例如，大範園的輻射使用長波長的光在技術上特別有可能。生產一種負性阻抗物質的特點之酸-敏感性成份類特別是當經由酸催化時（酸在輻射式I， la或lb的化合物時產生 )，能夠經歷一種與本身或與一種或多種组成物之進一步的成份進行交叉聯结反應的化合物類。此類化合物類為，例如，習知的酸-可熟化的樹脂類，如，例如，丙烯性，聚酯，醇酸，三聚氰胺，尿素，環氧化物及酚性樹脂類或其混合物類。胺基樹脂類，酚性樹脂類及環氧化物樹脂類為非常合適的。合此種型式之酸一可熟化的樹脂類通常為習知的且見述於，例如， Ullmann' s Encyclopadie der technischen Chemie， 4th Edition， Vo 1 . 1 5 ( 1 9 78) ，P. 613 - 628。該交叉聯结性成份類應該存在的濃度為 -45- 本紙張尺度適用中國國家揉準（CNS ) A4规格（210X297公釐） ---------—裝------訂------線 (請先聞讀背面之注意事項再填寫本頁) 經濟部中央標準局負工消費合作社印袋 A7 B7 五、發明説明（自重量百分比2至40，偏好自5至30 ，重里係基於負性組成物中的全部固體含量。特別是偏好作為酸一可熟化的樹脂類為胺基樹脂類，如非-醚化的或醚化的三聚氰胺，尿素，胍或二縮脲樹脂類，特別是甲基化的三聚氰胺樹脂類或丁基化的三聚氰胺樹脂類，相對應的甘脲類（glycolurils)及脲鉻類。在本文中，樹脂類應被瞭解為慣用的技術性混合物類，其通常亦包括寡合物類，K及純的及高純度化合物類。N—甲氧基甲基三聚氰胺及四甲氧基甲基甘脲（glucouril)及N，Ν' 一二甲氧基甲基脲鎗為最偏好的酸一可熟化的樹脂類。式 1· la或lb之化合物在負性阻抗物中的濃度通常自重量百分比0.1至30，偏好達到20，重量同樣係基於組成物類中的全部固體含量。重量百分比自1至15為特別偏好的。當合適時，負性組成物類可額外地包括薄層-形成性聚合性膠黏劑。該膠黏劑偏好為一種鹸一可溶性酚性樹脂。非常適合此目的者為*例如*酚醛清漆類，其衍生自一種醛，例如乙醛或糠基醛，但特別是衍生自甲醛，及一酚，例如未經取代的酚，單——或二一氮取代的酚*如p—氯酚，酚，其經由“ _C9烷基進行單--或二一取代，如0 -4 6 _ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） — I— I I 裝— — I I I I I n I I n 線 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央棣準局貝工消費合作社印装 A7 _B7_五、發明説明（0) 一，m—或P—甲酚，各式二甲苯酵類，P—第三一丁基酚，P -壬基酚，p—苯基酚，間苯二酚，雙（4一羥基苯基 )甲烷或2，2—雙（4一羥基苯基）丙烷。亦為合適的是基於伸乙基性不飽和的酚類之高一及共一聚合物類，例如乙烯基一及1一丙烯基一取代的酚類，如P—乙烯基酚或P—( 1-丙烯基）酚之高聚合物類或這些酚類與一種或多種伸乙基性不飽和的材料類，例如苯乙烯類，之共聚合物類。膠黏劑份量通常為重量百分比自30至95或偏好為重量百分比自4 0至8 0 0 本發明因此包括的一特別事實為，如上文已述者，負性，驗一可顯影的光阻物質類K供波長超過3 9 0微笔米之工作性輻射，其包括如上述之式I， la或lb肟磺酸酯，一種鹼一可溶性酚性樹脂作為膠黏劑及一種經由酸催化可以經歷與本身及/或與膠黏劑發生交叉聯结反懕之成份。負性阻抗物霣之一特別偏好的形式包括重量百分比 1 至 15的肟磺酸酯，重量百分比自40至99之酚性樹脂作為膠黏劑，例如前文所述者其中之一，及重量百分比自 0.5 至30之三聚第胺樹脂作為交叉聯结劑，百分比係相閫於组成物之固體含量。K酚醛漆清或特別是Μ聚乙烯基酚做為膠黏劑時，得到的負性阻抗物具有特別良好的特性〇 -47- (請先閲讀背面之注意事項再填寫本頁) 裝· 訂線本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐）經濟部中央標準局貝工消費合作社印裝 A7 B7 五、發明説明04^) 肟磺酸酯類亦可作為光化學性可活化的酸產生者κ供在負性阻抗物系統中之，例如，聚（縮水甘油）甲基丙烯酸_類之酸-催化***叉聯结反應。此類交叉瞄结反應見述於，例如，Chae 等人， Pollino 1 9 9 3，17 (3 )， 2 9 2 。為鹼-不溶性但可在酸的存在下被切割，或能夠分子内重排之單體性或聚合性化合物類，產生一種在根據本發明之光阻物質組成物類中的正性特徵。此類物質在後文被稱為溶液抑制劑類，在此種方式中，反應產物在一慣用的撖性顯影劑維持為可溶的及/或引起其他驗一不溶性及酸一抗性額外的膠黏劑在顯影劑中變成可溶的。如前文所指出，本發明因此包括的進一步特別的具髏事實為正性鹼性-可顯影的光阻物質類以供波長超過3 90微毫米之工作性輻射，其包括式I，la或lb之化合物及至少一種基本上防止組成物被溶於一鹼性顯影劑，但可Μ在酸的存在下被切割的化合物，在此種方式中，反應產物在一慣用的鹼性顯影劑維持為可溶的及/或引起一酸-抗性額外的膠黏劑，其於其他條件下在顯影劑中為不溶的，變成在顯影劑中為可溶的。 ~ 4 8 * 本紙張尺度逋用中國國家揉準（CNS ) Α4规格（210Χ297公釐） I 裝 . 訂線 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央橾準局員工消費合作社印裝 A7 B7 五、發明説明可為溶疲抑制劑類之單體性及聚合性有機化合物類所具有的官能性基團本身在一驗性基質中為可溶的，例如芳香性羥基基圈類，羧酸基團類，二级胺基基圑類及酮或醛基團類，但是他們已經由與一不溶於水性鹼中之合適的化合物進行反應而被化學性改變，在提及的反應中所形成的保護性基團類能夠經由酸催化反應再一次被切割，其方式為該官能性基團類被恢復成為原來的形式。為了保護羥基基團類，羧酸基團或二級胺基基團類為合適的為，例如，二氫呋喃或3，4一二氫砒喃及其衍生物類，苄基鹵化物類，烷基鹵化物類，鹵乙酸，鹵乙酸酯類，氯碳酸酯類，烷基磺醢基鹵化物類，芳香性磺醢基鹵化物類，二碳酸二烷基酯類或三烷基矽烷基鹵化物類，該反應有可能以已知的方式形成被保護的衍生物類。慣用的成為醛類及乙醛類的轉變作用合適於保護酮及醛基團類。此種化學性效果擴大正性咀抗物系統見逑於，例如， E. Reichmanis » F. M. Houl ihan * 0. JJalanasu， T. X. Neenan * Chen. Hater. 19 91* 3， 3 9 4 ;或 C. G. Willson，’’ Introduction to Micrography * 2nd.(V) V. Description of the invention 2.2 -Hydroxybenzophenols, such as 4-monohydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyl Oxygen, 4,2 ', 4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives 3. Unsubstituted or substituted benzoates, such as salicylic acid 4 -Third-butyl-phenyl ester, phenyl salicylate, octyl phenyl ester, dibenzylfluorenyl resorcinol, bis (4-tert-butylbenzylfluorenyl) resorcinol , Benzylidene resorcinol, 3,5-di-tri-butyl-4-hydroxybenzoic acid 2,4-di-tertiary-butylphenyl ester, 3,5-di-tertiary- Butyl_4-hydroxybenzoic acid hexadecyl ester, 3,5-di-tri-butyl benzoic acid octadecyl ester, 3,5-di-tri-butyl-4 Monohydroxybenzoic acid, 2-methyl-1,6-dione-tertiary-butylphenyl ester. 4Ester esters, such as α-cyano * / 3-diphenyl acrylate ethyl and isooctyl, α-carbomethoxyphenyl acrylate, α_cyano-di-monomethyl- ρ—methyl and butyl methoxyphenyl acrylate, α-carbomethoxy-P _ methoxyphenyl methacrylate and N — (yS — carbomethoxy — cyanovinyl 3 — 2-Methylindololine 5. Stereoscopically hindered amines, such as bis (2,2,6,6-tetramethylpiperidinyl) sebacate, bis (2,2,6,6-tetramethyl) Aminopyridinyl) succinic acid, bis (1,2,2,6,6-pentamethylmethylpyridinyl) sebacic acid, bis (1, -37-) This paper applies Chinese National Standard (CNS) A4 Specifications (210X297 mm) -------- 1 ^ ------ 1T ------ ^ (Please read the precautions on the back before filling out this page) Staff Consumption of the Central Bureau of Standards, Ministry of Economic Affairs Cooperative printed by the China Economic Standards Bureau of the Ministry of Economic Affairs. Printed by the Consumer Cooperative of the A7, B7. 5. Description of the invention (), 2,6,6_pentamethylstearyl) η-butyl-1,3-5-2nd third — Butyl-4 monohydroxybenzylmalonate, 1 monohydroxyethyl-2, The product of the condensation reaction of 2,6,6 —tetramethyl-1 4-hydroxyimidimidine and succinic acid, N, N′-bis (2,2,6,6-tetramethyl-4 4-piperidinyl) Condensation reaction products of hexamethylene diamine and 4-tris-octylamino-2,6-diaza-1,3,5-s-triple exposure, see (2,2,6,6 —Tetramethyl-1,4-piperidinyl) nitrinotriacetic acid, (2,2,6,6-tetramethyl-1,4-piperidinyl) 1,2,3,4-butanetetracarboxylic acid, 1, Guang— (1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazine_), 4-benzylfluorenyl-2,2,6 * 6-tetramethyl Piperidine, 4-stearylmethyloxo-2,2,6,6-tetramethylmethylpyridine, bis (1,2,2,6,6-pentamethylpethenyl) 2-Π-butyl A 2- (2-Cyclo-3,5-di-tertiary-butylbenzyl) malonate, 3-η-octyl-7,7,9,9-tetramethyl_1,3, 8-triazaspiro [4.5] decane-2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidinyl) sebacate, bis (1-1 Octyloxy-2,2,6,6-tetramethylpyridinyl) succinic acid, N, N'-bis ( Association of 2,2,6,6-tetramethyl-1,4-pyridinylhexamethylenediamine with 4-morpholinyl-2,6-dichloro-1,3,5-triazine Product, 2-Gas-4,6-Di (4-a-butylaminoamino-2,2,6,6-tetramethylpyridinyl) 1,3,5-triazine and 1,2-bis The product of condensation reaction of (3-aminopropylamino) ethane, 2-ammonium 4,6-di (4-η-butyllimyl-1,2,2,6,6-pentamethyl Piperidinyl) —The product of the condensation reaction of 1,3,5-triazine with 1,2-bis (3-aminopropylamino) ethane, 8-ethenyl-dodecyl- 7, 7, 9, 9 -3 8-This paper uses China National Standards (CNS) Α4 size (210 × 297 mm) --------- 1 race ----- 1T-- ---- (Please read the note $ on the back and fill in this page first) A7 B7 printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (j /) 141-methyl-1, 3, 8-triazaspiro [4.5] decane-2,4-difluorene, 3-dodecyl-1 1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine Mono 2,5-dione, 3-dodecane The radical 1-1 (1,2,2,6 * 6-pentamethyl-1 4-neosyl) This tower is steep -2,5-dione. 6. Ethylenediamines, such as 4,4'-dioctyloxyethylenedibenzidine, 2,2'-diethoxyethylenedibenzidine, 2,2'-dioctyloxy— 5,5_di-tertiary-butyl ethylenedianilide, 2,2'-docosalyl-5,5'-di-tertiary-butyl ethylenedifluoride, monoethoxy 2′-Ethylethylenedianilide, N, N′—Bis (3-dimethylaminopropyl) ethylenediamine, 2-Ethoxy-5—Third-Butyl-1 2'-Ethylethylenedianilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tri-butylethylenedianilide, and 0- and P —Methoxy- and 0- and P-ethoxy-disubstituted ethylenedifluorfenanilides. 7.2- (2-hydroxyphenyl) -1,3,5-triazines, such as 2, 4, 6-ginseng (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine , 2-(2-hydroxy-4-octyloxyphenyl) _4,6-bis (2,4-dimethylphenyl)-. 1,3,5-diphone, 2- (2,4— Diphenyl phenyl) — 4,6_bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4 4-propyloxyphenyl) —6— (2,4-Dimethylphenyl) -1,3,5-triazine, 2— (2-hydroxy-4 monovinyloxyphenyl-39-) This paper uses the Chinese national standard ( CNS) Α4 Washing (210X297mm) Gutter (please read the precautions on the back before filling this page) Printed by A7 B7, Shellfish Consumer Cooperative, Central Standards Bureau of the Ministry of Economic Affairs 5. Description of Invention (%) _4, 6 — Bis (4-monomethylphenyl) -1,3,5-triazine, 2- (2-monohydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethyl) Phenyl)-1 * 3,5-triazine, 2_ [2-Hydroxy-4-((2-hydroxy-3-butyloxypropyloxy) phenyl]-4,6-bis 2,4-dimethylphenyl) -1,3,5-triamidine, 2- [2-controller-4 4- (2-controller-3—octyloxy-propyloxy) phenyl] -1 4,6—bis (2,4-dimethylphenyl) -1,3,5-triazine and 2- [4-dodecyl / tridecanefluorenyloxy (2-hydroxypropyl) oxy-1 2-hydroxyphenyl] -4,6-bis (2,4-dimethyl-phenyl) 1,3,5-triazine. 8. Phosphites and phosphonates, such as triphenyl phosphite, alkyl diphenyl phosphite, dialkyl phenyl acid, diphenyl phosphite (nonylphenyl) Esters * trilaurylphosphonium phosphite, tris (octadecyl) phosphite, tetrapentaerythritol diisolipidyl diphosphite, ginseng phosphite (2,4_two one three one Butylphenyl) ester, diisodecyl diphosphite-tetrapentaerythryl ester, tetrapentaerythritol diphosphite bis (2.4-di-tris-butylphenyl) ester, diphosphite Tetrapentaerythryl phosphate bis (2,4_-di-tri-butyl-4-methylphenyl) ester, diisodecyloxy diphosphite-tetrapentaerythryl phosphate, diphosphite Fourth pentaerythritol bis (2,4-di-tri-butyl-6-methyl-phenyl) ester * diarsinic acid Tertiary butyl phenyl) ester, sorbitan triphosphite stearyl sulfonyl ester, bis- (2,4 1,2 tertiary butyl phenyl) -4, 4 'diphenylene diimide Phosphate, 6-isooctyloxy-2,4,8, -40- This paper uses China Furniture rate (CNS) Α4 grid (210 × 297 mm) ---------------, order -------- ^ (Please read the precautions on the back before filling in this Page) Printed A7 £ 7_ by the Central Bureau of quasi-Ministry of Economic Affairs of the People's Republic of China 5. Description of the invention "]) 10-tetra-t-tri-butyl- 12H-dibenzyl [d, g] -1,3,2 -Dioxophosphocine, 6-Ga-2,4,8 '10 -tetra-second-butyl-12-methyl-dibenzyl [dg] -1,3,2-dioxophosphocine, sub Bis (2,4-di-tri-butyl-6-methylphenyl) methyl phosphate and bis (2,4-di-tri-butyl-6-methylphenyl) phosphite Ethyl esters. Such light stabilizers can also be added, for example, a coating layer on an adjacent surface gradually diffuses from the layer of light stabilizers into the baking paint layer to be protected. A coating layer on the adjacent surface may be a baking paint. The original layer under the layer or the finishing paint on the baking paint layer. It is also possible to add to the resin, for example, photosensitizers, which transfer or increase the spectral sensitivity, so that the radiation period can be shortened and / or used Other light sources. Light Examples of sensitizers are aromatic ketones or aromatic aldehydes (see, for example, US Pat. No. 4,017,652), 3-fluorenyl-coumarins (see, for example, US Pat. No. 4,366) 228), 3 — (Arylamidomethylene) -Sialazolins, Sulfurs, Condensed aromatic compounds, such as perylene, aromatic amines (see described in, For example, US Patent 4 069 954) or cationic and basic colorants (see, for example, US Patent 4 Q26 705), such as eosin, rhodanine and erythrosine colorants Class. -4 1- This paper size is applicable to China National Standards (CNS) Standard 8 (210X297) 漦 -------- TP # ------ IT ------ ^ ( Please read the notes on the back before filling in this page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Printed by the Bayer Consumer Cooperative A7 B7 V. Description of the Invention Other conventional additives-as intended-Optical brighteners, fillers , Pigments, colorants, wet tinctures or fluidity improvers. In order to cure thick and doped pigmented coatings, micro glass beads or powdery glass beads, which are described in US-A-5 013 768, are suitable. Other examples of additional light starters or additives have been described above. Oxime sulfonates can also be used, for example, in hybrid systems. These systems are based on formulations that are cured by two distinct reaction mechanisms. Examples are systems that include components capable of undergoing an acid-catalytic cross-linking reaction or a polymerization reaction, and also include further components that can be cross-linked via a second mechanism. Examples of the second mechanism are, for example, complete radical curing, oxidative cross-linking or moisture-start cross-linking. The second ripening mechanism can be initiated simply by heating * if necessary, using a suitable catalyst, or via light using a second light starter. According to the present invention, in addition to component c) M, the photo-activatable composition may further include photo-starters, sensitizers and / or additives, or compounds of formula I, la or lb. The combination of light starters, sensitizers and / or additives. -42- This paper size applies to Chinese National Standards (CNS) (210X297mm) II — — — — IIIIII n ^ 1 line (please read the precautions on the back before filling this page) Consumption by the Central Bureau of Standards, Ministry of Economic Affairs Cooperative printed A7 B7_ V. Description of the invention (1) If the composition includes a free cross-linkable component, the curing method, especially for the composition of doped pigments (such as the use of titanium dioxide), can also be added by means of Free radical-forming ingredients under thermal conditions, such as an azide compound, such as 2,2-azidebis (4-methoxy-2,4-dimethylvaleronitrile), triazene (triazene ), Diazide sulphite, pentazadiene or a peroxy compound * such as * For example, hydrogen peroxide or peroxy carbonate, such as tert-butyl hydrogen peroxide, which is described in, For example, EP-A245639. Adding kangan oxidizing starters, such as cobalt salts, allows aging to be oxidatively cross-linked by means of oxygen from the air. The surface coating can be applied by a method customary in the art, such as by spraying, painting or immersion. It is also possible when using suitable surface coatings * to apply electronically, for example by electro-immersion coating. After dry kneading, a thin layer of surface coating was shot. If necessary, the thin layer of surface coating is fully cured by heat treatment. The compounds of the formulae I, la and lb can also be used for curing molded articles made from composites. A composite includes a self-supporting matrix material, such as a glass follower, which is embedded with a M photothermal formulation. The anti-substance system can include formula I, la or lb-43 through image-by-image radiation. The paper size is applicable to the Chinese national standard (CNS) A4 (210X297 mm) ---------- Γ Packing ------ order ------ line (please read the notes on the back of the 锖 first and then fill out this page) Printed by the Central Working Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, A7 B7__ V. Description of the invention ((// : 0) A system of compounds, followed by a developing step. As already mentioned, compounds of formulae 1 'la and lb can be used as a light-sensitive acid provider in a photoresist, especially for Radiation with a wavelength exceeding 390 micrometers. The present invention is accordingly also related to a photoresist 霣 K for radiation with a wavelength exceeding 390 micrometers, which is based on the oxime sulfonate as a photosensitive acid provider, the photoresist , Including compounds of formula I, la or lb as oxime sulfonates. The difference in solubility between the irradiated and non-irradiated parts occurs because the impedance material is on or after the radiation of the impedance substance The acid-catalytic reaction can be of two types. As a result of this, further components appear in the impedance Substance. If the composition of the present invention includes a component that enhances the solubility of the composition in the developer after irradiation, the resistance substance is positive. If, on the other hand, these components can reduce the composition after radiation The soluble component in the developer, the resistive substance is negative. The present invention accordingly also relates to a negative photoresistive substance and a positive photoresistive substance. The oxime sulfonic acids of the formula I, la and lb Ester can also be used as a chemically amplified resist. A chemically amplified photoresist is known as a photosensitive component of a resistive substance composition. After being irradiated, it provides only those materials that need to catalyze the resist. The acid content of the chemical reaction of at least one acid-sensitive component-4 4-This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) --------- Package ----- -1T ------ ^ (Please read the precautions on the back before filling out this page), A7 B7 printed by the Shellfish Consumer Cooperative of the Central Bureau of Samples of the Ministry of Economy Develop the most intermediate between irradiated and non-irradiated areas Different solubility. The present invention is accordingly also related to a photoresistive substance with a chemical expansion effect. This kind of resistive substance shows an obvious lithographic sensitivity to long-wavelength radiation, especially radiation exceeding 390 micrometers. The photoresist substances according to the present invention have excellent lithographic characteristics, especially high sensitivity, and they also have the advantage of reacting with radiation in the near UV range. The radiation in the near UV range is basically more technical from a technical point of view. Easy to use. For example, the use of long-wavelength light is particularly technically possible for Dafanyuan's radiation. The acid-sensitive components that produce the characteristics of a negative impedance material are especially when catalyzed by acids (acids in radiative form I , La or lb compounds), compounds that can undergo a cross-linking reaction with itself or with one or more further components of the composition. Such compounds are, for example, conventional acid-curable resins such as, for example, acrylic, polyester, alkyd, melamine, urea, epoxide, and phenolic resins or mixtures thereof. Amine resins, phenol resins and epoxide resins are very suitable. Acid-curable resins of this type are commonly known and described in, for example, Ullmann's Encyclopadie der technischen Chemie, 4th Edition, Vo 1. 15 (1 9 78), P. 613- 628. The concentration of this cross-linking component class should be -45- This paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) ----------- packing ------ Order ------ line (please read the notes on the back before filling out this page) Printed bags A7 B7 of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (self-weight percentage 2 to 40, preference from 5 To 30, based on the total solids content of the negative composition. Especially preferred as the acid-curable resins are amine-based resins, such as non-etherified or etherified melamine, urea, guanidine or diamine. Urea resins, especially methylated melamine resins or butylated melamine resins, the corresponding glycolurils and urea ureas. In this article, resins should be understood as the conventional technology Mixtures, which usually also include oligomers, K and pure and high purity compounds. N-methoxymethyl melamine and tetramethoxymethyl glycoluril (glucouril) and N, N'-dimethyl Oxymethylurea guns are the most preferred acid-curable resins. Formula 1.la or l The concentration of the compound b in the negative impedance is usually from 0.1 to 30% by weight, with a preference of 20, and the weight is also based on the total solids content of the composition. The weight percentage from 1 to 15 is particularly preferred. When appropriate The negative composition may additionally include a thin layer-forming polymerizable adhesive. The adhesive is preferred to be a soluble phenolic resin. Very suitable for this purpose are * for example * novolacs, which are derived From an aldehyde, such as acetaldehyde or furfural, but especially derived from formaldehyde, and monophenols, such as unsubstituted phenols, mono- or di-nitrogen substituted phenols * such as p-chlorophenol, phenol, Mono- or di-one substitution via "_C9 alkyl", such as 0 -4 6 _ This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) — I— II equipment — — IIIII n II n wire (Please read the notes on the back before filling out this page) Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Shellfish Consumer Cooperative, A7 _B7_V. Description of the invention (0) One, m- or P-cresol, all kinds of xylene fermentation Class, P-tertiary-butylphenol, P-nonylphenol, p- Phenol, resorcinol, bis (4-hydroxyphenyl) methane or 2,2-bis (4-hydroxyphenyl) propane. Also suitable are phenols based on ethylenically unsaturated phenols. And co-polymers, such as vinyl- and 1-propenyl-substituted phenols, such as P-vinylphenol or P- (1-propenyl) phenol high polymers or these phenols with one or Copolymers of various ethylenically unsaturated materials, such as styrenics. The amount of adhesive is usually from 30 to 95% by weight or preferably from 40 to 80% by weight. The invention therefore includes A special fact is that, as already mentioned above, a negative, developable photoresist substance K is provided for working radiation with a wavelength exceeding 390 micrometers, which includes formula I, la or lb as described above. Oxime sulfonate, an alkali-soluble phenolic resin as an adhesive and an ingredient that can undergo cross-linking with itself and / or with the adhesive via acid catalysis. One of the particularly preferred forms of negative resistance compounds includes oxime sulfonates from 1 to 15 weight percent, phenolic resins from 40 to 99 weight percent as adhesives, such as one of the foregoing, and weight percent Trimeric diamine resins from 0.5 to 30 are used as cross-linking agents, and the percentage depends on the solid content of the composition. When K phenolic varnish or M polyvinyl phenol is used as an adhesive, the obtained negative impedance has particularly good characteristics. 〇-47- (Please read the precautions on the back before filling this page) The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm). Printed on A7 B7 by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention 04 ^) The oxime sulfonate can also be used as a photochemical agent. Activated acid producer κ is provided in negative impedance systems, for example, poly (glycidyl) methacrylic acid-catalyzed cross-linking reactions. Such cross-knot reactions are described in, for example, Chae et al., Pollino 1 9 9 3, 17 (3), 2 9 2. Monomeric or polymeric compounds that are base-insoluble but can be cleaved in the presence of an acid, or that can be rearranged intramolecularly, produce a positive feature in the photoresist composition composition according to the present invention. Such substances are hereinafter referred to as solution inhibitors. In this manner, the reaction product remains soluble in a conventional alkaline developer and / or causes other tests to be insoluble and additional acid-resistant. The adhesive becomes soluble in the developer. As pointed out previously, the invention further includes a further particular cross-cutting fact that it is a positive alkaline-developable photoresist substance for working radiation with a wavelength exceeding 3 90 micrometers, which includes formula I, la or lb. Compound and at least one compound which substantially prevents the composition from being dissolved in an alkaline developer, but which can be cleaved in the presence of an acid. In this manner, the reaction product is maintained in a conventional alkaline developer as Soluble and / or causing an acid-resistant additional adhesive, which is insoluble in the developer under other conditions, and becomes soluble in the developer. ~ 4 8 * This paper size is in accordance with China National Standard (CNS) Α4 size (210 × 297 mm) I Packing. Thread (please read the precautions on the back before filling this page) Staff Consumer Cooperative of the Central Procurement Bureau of the Ministry of Economic Affairs Printed A7 B7 5. Description of the Invention The functional groups that can be monomeric and polymerizable organic compounds that are solubilizers are soluble in a test matrix, such as aromatic hydroxyl groups Compounds, carboxylic acid groups, secondary amine groups, and ketone or aldehyde groups, but they have been chemically altered by reaction with a suitable compound insoluble in an aqueous base, as mentioned in the The protective groups formed during the reaction can be cleaved again via an acid-catalyzed reaction in such a way that the functional groups are restored to their original form. In order to protect the hydroxyl group, a carboxylic acid group or a secondary amine group is suitable, for example, dihydrofuran or 3,4-dihydrofuran and derivatives thereof, benzyl halide, Alkyl halides, haloacetic acid, haloacetates, chlorocarbonates, alkylsulfonyl halides, aromatic sulfonyl halides, dialkyl dicarbonates or trialkylsilyl groups Halides, this reaction has the potential to form protected derivatives in a known manner. The usual conversion to aldehydes and acetaldehydes is suitable for protecting ketones and aldehyde groups. This kind of chemical effect enlarges the positive mouth antibody system. For example, E. Reichmanis »FM Houl ihan * 0. JJalanasu, TX Neenan * Chen. Hater. 19 91 * 3, 3 9 4; or CG Willson, '' Introduction to Micrography * 2nd.

Ed . ; L. S. Thompson， C. G. Willson * M J. Bowden ，Eds. » Anier. Chem. Soc.， Washington DC * 1994， P . 139° -49- 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐） ---------Γ裝------訂------線 (請先閲讀背面之注意Ϋ項再填寫本頁) 經濟部中央標準局員工消費合作杜印装 B7 五、發明説明（f) 在已述類別的正性阻抗物中，一薄層-形成性，聚合性溶液抑制劑可為唯一在光阻物質中的膠黏劑或可與一酸一惰性膠黏繭及，當合適時，一種軍體性溶液抑制劑Μ混合物的方式使用。酸-惰性膠黏劑類之實施例為酚醛清漆類，特別是基於〇—， m —或Ρ-甲酚及甲醛者，亦為聚（ρ—羥基苯乙烯）*聚（P_羥基一 α —甲基苯乙烯）及Ρ—羥基苯乙烯， Ρ-羥基一 α _甲基苯乙烯及乙醢氧基苯乙烯之共聚合物類。聚合性溶液抑制劑類之實施例為酚醛清漆類，特別是基於〇— * m —或ρ—甲酚及甲醛，聚（ρ -羥基苯乙烯） *聚（P —羥基一α —甲基苯乙烯），Ρ —羥基苯乙烯或Ρ — 羥基-α -甲基苯乙烯與乙醯氧基苯乙烯或丙烯性酸及/ 或甲基丙烯酸及（甲基）丙烯酸酯類之共聚合物類，其以習知的方式與二氫呋喃，3· 4—二氫吡喃*苄基鹵化物類，烷基鹵化物類，鹵乙酸，鹵乙酸酯類，氛碳酸酯類，烷基磺醢基鹵化物類，芳香性磺醢基鹵化物類，二碳酸二烷基酯或三烷基矽烷基鹵化物類進行反應。亦為合適的是聚合物類 Ρ_ (2 —四氫毗哺基）一氧苯乙烯或Ρ—(第三_ 丁基氧羰基）一氧苯乙烯與（甲基）丙烯性酸* (甲基） -50- 本紙張尺度適用中固國家揉準（CNS ) Α4規格（2丨〇X297公釐） ----------—^------ΐτ------^ (請先聞讀背面之注意Ϋ項再填寫本頁) 經濟部中央標準局員工消費合作社印聚 A7 B7__ 五、發明説明（《2) 丙烯性酸酯類及/或 P-乙醢基苯乙烯之聚合物類及p-羥基苯乙烯及/或P_ ( 2—四氫毗喃基）一氧苯乙烯與 3 -羥基苄基（甲基）丙烯酸酯類之聚合物類，若有需要，其可額外地經由與上列化合物類之進行反應而被保護。特別是合適的是在波長範圍自180至1000微毫米為透明的且攜帶兩種在酸催化性去保護作用後帶來溶解性改變之基圑類之聚合物類，及增加酸產生者之溶解性及確保水性驗性可顯影性的厭水性及親水性基匾類。此類聚合物的實施例為丙烯酸酯類及甲基丙烯酸酯類，其經由共一或三 -聚合作用自相對應的單體進行製備。該類單體亦可攜帶有機矽自由基以便，例如，在乾蝕方法中增加抵抗性。單體類的實施例為：（甲基）丙烯酸甲酯，（甲基）丙烯性酸，（甲基）'丙烯酸第三一丁基酯，（甲基）丙烯酸三甲基矽烷基甲基酯* (甲基）丙烯酸3—氧環己基酯，（甲基 )丙烯酸四氫吡喃酯，（甲基）丙烯酸金剛烷酯，環己基 (甲基）丙烯酸酯，（甲基）丙烯酸諾伯基（norbornyl)酯。本發明據此亦相關於一種化學性效果擴大正性咀抗物質，其包括作為感光性酸提供者之一種式I， 13或11)之化合物。特別偏好的是一種化學性效果擴大正性阻抗物質，其包括作為感光性酸提供者之式lb之化合物。 -5 1- 本紙張尺度遑用中國國家標準（CNS ) A4規格（210X297公釐〉 — I I I ——— — —— 裝訂線 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消费合作杜印装 A7 B7_ 五、發明説明（#) 本發明亦相鼷於一種光阻物質’其包括的聚合物類在達波長區域1 80微毫米時為透明的。根據本發明之正性阻抗物質之特別的具體事實包括重量百分比自 75至99.5之一種薄層一形成性聚合物，其包括可經由酸催化作用去除的保護性基團類*及重量百分比自 0 .5至25之式I，la或lb之肟磺酸酯類，百分比係基於組成物類中的固體含量。在此方面，偏好的組成物類包括重量百分比自 80至93之已述聚合物及重量百分比自 1至20之肟磺酸。另一個具體事苴為一種正性阻抗物質，其包括重量百分比自40至90之酸-惰性薄層一形成性聚合物作為膠黏劑，重量百分比自5至40之一單體性或聚合性化合物，其具有可被酸催化作用去除的保護性基團類，及重量百分比自0. 5至 25之式I， la或lb之肟磺酸酯類，百分比係相闞於组成物類中的固歷。這些組成物類中偏好者為包括重量百分比自 50至85之酸一惰性膠黏劑，重量百分比自 10至30之單體性或聚合性溶疲抑制劑及重量百分比自1至15之肟一磺酸酯類。肟磺酸酯類亦可作為光一可活化的溶解性促進劑類。在此種情形下，化合物被加至一薄層-形成性材料，其本 -52- 本紙張尺度適用中國國家橾準（CNS ) A4規格（210X297公嫠） ---------Γ裝------訂------線 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印«. A7 £7_ 五、發明説明（j ) 霣上不包括加熱時或κ動力性輻射進行輻射時可與肟磺酸酯聚合的成分。然而，該肟磺酸酯類降低薄層-形成性材料溶解於一合適的顯影劑介值的速度。此種促進效果可Μ 經由將該混合物Κ動力性輻射進行輻射而抵銷，所以可以產生一正性影像。此種應用見述於，例如， ΕΡ- Α— 241 4 2 3 〇最後，本發明之進一步特別的具體事實為一種正性阻抗物質，其包括一種式 1， la或lb之化合物及一種膠黏劑，其本質上不溶於一種鹼性顯影劑且在式 1， la或lb 之化合物的光解產物存在下變成可溶解的。在此倩況下已述之肟磺酸酯化合物的份量通常為重量百分比自 5至50 ，其基於該組成物之固體内含物。根據本發明之肟磺酸酯類用於化學性效果擴大系統，該系統基於自一聚合物移除保護性基團的原則運作，通常產生一種正性阻抗物。正性阻抗物與為偏好的負性阻抗物比較在許多方面都為偏好的，特別是因為其較佳的解像力。然而，使用正性阻抗物質機制亦有利於生產負性影像，以便整合正性阻抗物質之高度解像力的優點及負性阻抗物的特性，其可經由導入所謂的像-翻轉步驟而達成，該步驟見述於，例如，EP-A-361 906。為此目的，在顯影步驟前將進行逐像輻射的阻抗物質材科以，例如，一種氣 -5 3 - 本紙張尺度適用中國國家橾準（CNS ) Α4規格（210Χ297公釐） ,»* --------------^.1 艮------______泉 (請先閱讀背面之注意事項再填寫本頁) 擎經濟部中央橾準局員工消费合作社印製 A7 £7_ 五、發明説明（p) 體狀驗加以處理，使得產生之逐像酸可Μ被中和。随後，進行全區域之第二次鞴射及熱後處理且負性影像以慣用的方式予以顯影。除了已述之组成分以外，負性及正性光阻物質組成物類可額外地包括一種或多種在光阻物霣中慣用的添加物類，其份置為嫻於此技藝人士所熟習，例如流動性改良劑，濕濶劑類，黏著劑類，觸變劑類，著色劑類，色素類*填充劑類，溶解度加速劑等等。該反應可Κ經由加入光敏感劑類而加快速度，光敏感劑類可移動及/或加寬光頻敏感度，特別是芳香性羰基化合物類，如二苯甲酮，硫黃酮，趕颳及3_醢基香豆素衍生物類且亦為3—(芳醢基亞甲基）唾唑啉類，但亦可為伊紅，繞丹寧（rhodanine)及赤蘚紅（erythrosine)著色劑類. 為了應用，該組成物類必須包括一溶劑。合適的溶劑類的實施例為乙酸乙酯，丙酸3—甲氧基甲基酯，丙嗣酸乙酯，2—庚萌，二乙基乙二酵二甲基醚，環戊嗣，環己酮， 7 — 丁醢内酯，乙基甲基嗣，2—乙氧基乙醇，乙酸2 —乙氧基乙酯及特別是乙酸1-甲氧基-2_丙基酯。溶劑亦可為一混合物的形式，例如兩種或多種上述溶劑類。溶劑及其濃度的選擇，例如，視組成物的特性及被覆方法而定。 -54- 本紙張尺度適用中國國家榇牟（CNS ) A4規格（210X297公釐） ----------- 裝------1T------^ (請先閲讀背面之注意事項再填寫本I) 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明ti) 使習知的塗覆方法，將溶液均勻地拖於基質上，例如藉旋纺塗覆，浸漬塗覆，刀括塗覆，幕塗覆，刷塗*噴塗，以及逆滾塗覆。也可能將光敏層施於暫時的彈性支撐物上，然後藉由積層之層轉移塗覆最後的基質（層化）。施予數量（層厚度）和基質特性（被覆基霣）依所要應用而改變。塗覆厚度一般為約0.1微米到1〇〇微米K上。本發明的組成物可應作為電子光阻，如蝕刻阻抗物，電鍍阻抗物和焊錫阻抗物，製備積體霣路或薄層電晶體一阻抗物；TFT -阻抗物；製備印刷板，如膠板印刷板或網板印刷，用於模製物的蝕刻或立髓板石版印刷技術。塗覆基質和加工條件的範圍因此相當廣泛。本發明之組成物類為亦特別合適作為所有類別基質的塗覆基質，例如木材*坊绷物，紙，陶瓷，玻璃，塑膠，如聚酯，對苯二甲酸聚伸乙基酯，聚烯類或缵維素醋酸酯，特別是薄膜形式者，也包括金屬如鎳，鐵，鋅，鎂或鈷，或特別是銅及鋁，亦為矽或二氧化矽或亞硝酸矽，在基質上藉由逐像曝光形成影像。在被覆作業後，溶劑通常經由加熱移除，在該基質上得到一層光阻物質。乾燥的溫度必須低於使阻抗物質中的 -55- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） I 裝訂— I I I線 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消费合作社印製 Α7 Β7 五、發明説明成份可能被熱热化的溫度。所κ必須小心操作，特別是在負性光阻物霣的情形。通常，乾燥溫度不應超過 80 至 130t：〇該阻抗物霣被覆物随後進行逐像輻射。專有名詞"逐像（imagewise)輻射"包含K動力性辐射進行一預定形式的輻射，即，經由包含一預定形式的光罩進行顯影，例如一幻燈片* Μ及使用，例如，经由電腦控制之雷射光源於被覆基霣的表面移動，藉此產生一影像。在曝光及，若有須要，熱處理之後，該光姐抗物之未曝光區域（在正性光阻物質的情形下）或被輻射的區域（在負性光阻物質的情形下）使用顯影劑以本身為已知的方法加以去除。通常在顯影步驟之前需要一段時間讓阻抗物質組成物的酸一敏感性成份進行反應。為了加速該反應及因而在阻抗物質被覆物在顯影劑中在被輻射的及未被輻射的區域之間發展出有足夠差異的溶解度，被覆物偏好在顯影前進行加熱。加熱亦可在輻射時進行或開始。偏好使用自60 至 150Ό的溫度。時間的長短視加熱的方法而定及，若有需要 *最適合的時段可為嫻於此技藝者經由一些例行的實驗予 Μ簡易地決定。通常自數秒鐘至數分鐘。例如，使用加熱 -56- 本紙張尺度逋用中國國家標準（CNS ) Α4規格（210><297公釐） ---------Η 裝 II (請先閲讀背面之注意ί項再填寫本頁) 訂 A7 B7 經濟部中央標準局員工消費合作社印策五、發明説明（D) 1 1 I 板時，白 1( )至 3 0 0秒的時段為非常合適的；使用傳統烤 1 1 1 箱時 * 1至 30分鐘的時段為非常合適的。非常重要的 /—ν 1 I 請 1 1 是 t 在該阻抗物質上的非被輻射的位置之根據本發明之沉先閲 I I 讀 1 潛性酸提供者在這些加工條件下需為穩定的。背 1 之 1 注 | 意 I 被覆物随後被顯影，被覆物經過輻射後的位置在顯影事項 1 I 再 1 I / 劑中較易溶解而被去除。若有需要，工作物件的輕微搖動 4 窝本 I! 裝 » 輕刷在顯影劑浴中的被覆物或噴灑式顯影可Κ 加速加工頁 1 I 步驟〇慣用於阻抗物質技藝的水性一鐮性顯影劑類，例如 1 1 I * 可被用於顯影〇此類顯影劑包括，例如，氫氧化納或氫 1 1 氧化鉀相對應的碳酸鹽類，碳酸 Μ鹽類，矽酸鹽類或間 1 訂矽酸盥類但偏好為無金屬之鹼類，如氨或胺類，例如乙 1 I 基胺 η 丙基胺二乙基胺二一 η -丙基胺三乙基胺 1 I 9 甲基二乙基胺烷酵胺類，例如二甲基乙酵胺，三乙酵 1 1 胺四级数氫氧化物類，例如四甲基銨氫氧化物或四乙基 1 線銨氫氧化物 0 顯影劑溶疲類通常達 0.5 Ν 但是經常Κ合適 1 I 的方式在使用前加稀釋。例如正常下約 0 . 1 Ν 的溶液類為 1 I 合適的 0 顯影劑的選擇視光可熟化的表面被覆物的特性而 1 1 1 定 9 特別是視所使用的膠黏劑或得到的光解產物的特行而 1 1 定 0 水性顯影劑溶疲類 |若有需要，亦包括相當少量之濕 1 1 潤劑類及 / 或有機性溶劑類。可被加入顯影劑液體中的典 1 I 型有機性溶劑類為 f 例如，環己嗣 9 2- -乙氧基乙酵|甲 1 1 I 苯，丙酮 f 異丙酵以及這些溶劑類中兩種或多種的混合物 1 1 -57 - 1 1 本紙張尺度適用中國國家揉準（CNS )八4洗格（210X297公釐）經濟部中夬樣準局員工消費合作社印裝 A7 B7 五、發明説明（0) 類。典型的水性/有機性顯影劑系統係基於 Butylcellosolve®/ 水。由EP — A— 5 9 2 1 3 9中已知肟磺酸酯類在適於表面處理及清潔玻璃，鋁及餓表面的組成物類中可被用於作為光-可活化的酸產生劑類。這些化合物類在此種有櫬矽烷系統中的使用得到與使用游雄酸者相比具有明顯較佳的貯藏特性之組成物類。當與一在PH值改變會改變顔色的著色劑聯用時，肟磺酸酯類亦可用生產所諝〃印出（print — out)"影像，其見述於日本專利申請案 JP-A Hei 4 3 2 8 5 5 2或 US-A-5 2 3 7 059。此種色彩-轉變***根據EP-A- 199 672亦可用於監視對熱或輻射敏感的貨品。除了顔色的改變Μ外，在可溶性色素分子之酸一催化性去保護作用時有可能發生色素结晶沉澱；此可被用於生產色彩濾鏡。合適的交叉聪结包括式I， la或lb的化合物類的組成物類之辐射源為波長約自180至1000 ，例如自300至600 或偏好為自 380至600，例如自380至600微毫米之射出輻射。點光源及扁平輻射器（燈氈類）為合適的。實施 -58- 本纸張尺度適用中國圉家標準（CNS ) A4规格（210X297公釐） ! II _| 裝 I I I 訂— I ―― i I I 線 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央樣準局貝工消費合作社印袈 A7 B7_ 五、發明説明（<) 例為碳弧燈類，氙弧燈類，中等壓力，高壓及低壓水銀燈類，若有需要綴雜Μ金臞鹵化物類（金靥鹵素燈類），微波一刺激性金屬蒸氣燈類，激光燈類，超動性（ superactinic)螢光管，螢光燈類，白熾氰氣燈類，電動閃光類，照相性泛先（flood)燈類，電子束及X —射線類，其經由同步輻射，或雷射漿製造。介於燈及本發明之將被被覆之基質之間的距離可Μ視應用及燈的種類及/或功率而有所變化，例如介於2公分及1 5 (]公分之間。特別合適的是雷射光源，例如激光雷射類，如krypton F雷射供248 微毫米波長或Ar- F雷射供193微牽米波長之曝光。亦可使用在可見光範圍或适紅光範圃的雷射。最特別合適的為水銀h及g帶位於波長4 3 6及4Q5微毫米之輻射。合適的光源因此特別是水銀蒸氣燈，特別是中壓及高壓水銀燈，該輻射之其他波長的射出頻帶可依喜好予以瀘除，特別是在使用栢當短波長輻射的情形下。在燈及工作物件之間的距離，例如，可由2公分自150公分，其根據意欲用途及燈的類型及/或強度而定。然而，亦有可能使用低能量燈 (例如螢光燈管）•其能在合適的波長範圍中輻射，實例為 Philips TL03燈。合適的雷射一光束來源為，例如，氬離子雷射，其於波長 454， 458，466， 472， 478及 488 微毫米射出。亦為合適的是，例如，一氦/鎘雷射，其在442微奄米輻射或在UV範圍發射的雷射。使用此類輻射時，並沒有一定要使用與該光聚合性被覆物接觸的光罩 -59- 本紙張尺度適用中國國家橾準（CNS ) A4規格（210X297公釐） --------丨裝------訂------線 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作杜印裝 Α7 Β7 五、發明説明（rt) 來產生一正性或負性阻抗物；經控制的雷射光束能夠直接 "寫〃在被覆物上。為此目的，根據本發明之材料類的高敏感性是非常有利的，使得在相對低強度下有高"寫〃速度。在輻射時，表面被覆之被輻射區域中的組成物中的肟磺酸酯發生分解而形成磺酸。與慣用高強度輻射進行 UV熟化相反的是，使用根摟本發明的化合物類，活化在相當低強度的輻射下可以達成。此種輻射包括，例如，日光（陽光），及相當於日光的輻射源。陽光所使用的光譜組成物及強度與使用於V熟化之人工輻射源的光不同。根據本發明之化合物類的吸收特徵特別合適利用日光作為熟化所需輻射之自然來源。可K用於活化根據本發明的化合物類的日光相當的人工光源被理解為低強度的發射器，如一些螢光燈，例如Philips TL05 特別螢光燈或Philips TLO 9特別螢光燈。具有高日光成分的登或日光本身特別能夠令人滿意地K非钉固方式熟化一表面-被覆層的表面。在此情形下，昂貴的熟化儀器為多餘的且該組成物類可特別被用於Μ日光或日光相當的光源之外部完成性熟化，此為一種能源節省方法且防止在外部應用之揮發性有機性成份的發散。與適合扁平元件之輸送帶方法相反的是*日光熟化亦可用於靜態或被固定的物品及结構。 -6 0 - 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） (請先閲讀背面之注意事項再填寫本頁) 訂線經濟部中失標準局員工消费合作社印製 A7 B7_ 五、發明説明待热化的表面被覆物可直接曝於陽光或日光相當的光源下。然而*热化作用亦可發生於一透明層之後處（例如玻璃面板或塑膠薄片）。式I， la及lb之化合物類通常被加入該光可活化的組成物中的份量自重量0.1至30 %，例如重量自0·5至 10%·特別是重量自1至5%。本發明亦相關式I，la及lb之化合物類，其在用於生產表面被覆物類，印刷油墨類，印刷板類，齒科组成物類，色彩過濾物類，阻抗材料類或影像記錄性材料類，或供記錄全影成像之影像記錄性材料類時，作為感光性酸提供者 Μ供波長超過390撤毫米之輻射。下列實施例進一步示範本發明。在後面的說明書及專利申請專利範圍中，除非另有說明，份或百分比的數據係基於重量而言。實施例 1: ct_ (甲基苯基磺醢基氧亞胺基）一 3，4 —二甲氧基苄基氰化物 1.1 α —羥基亞胺基一3，4一二甲氧基苄基氛化物 -6 1- 本紙張Λ度適用中國國家標準（CNS ) Α4规格（210X297公釐） I--------^1 —------1Τ------.^. (請先閲讀背面之注意Ϋ項再填寫本頁) 經濟部中央標準局員工消費合作社印製 A7 B7___ 五、發明説明（L^f) 47 公克（1.17莫耳）之NaOΗ，其被溶解於450毫升之甲酵中，被加入於一磺化用錐形瓶中的208.03公克（ 1.17 莫耳）之3，4一二甲氧基苄基氣化物且該溶液於一冰一浴中冷卻至0—5Ό。在此溫度下，進行攪拌4小時後，將1. 17莫耳之氣趙狀亞硝酸甲酯（經由將 38奄升之灃 Hz S04 ，其溶解於82毫升之水中，加到 97.1 公克之Ed.; LS Thompson, CG Willson * M J. Bowden, Eds. »Anier. Chem. Soc., Washington DC * 1994, P. 139 ° -49- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 (Mm) --------- Γ installed ------ order ------ line (please read the note on the back first and then fill out this page) Employees of the Central Standards Bureau of the Ministry of Economy Du Yinzhuang B7 V. Description of the Invention (f) In the category of positive resistance mentioned above, a thin layer-forming, polymerizable solution inhibitor can be the only adhesive in the photoresist substance or can be used with a Acid-inert glue cocoons and, where appropriate, a mixture of military solution inhibitors M are used. Examples of acid-inert adhesives are novolacs, especially those based on 0-, m-, or P-cresol and formaldehyde, also poly (ρ-hydroxystyrene) * poly (P_hydroxy-α —Methylstyrene) and P-hydroxystyrene, P-hydroxy-α-methylstyrene and ethoxylated styrene copolymers. Examples of polymerizable solution inhibitors are novolacs, especially based on 0- * m- or ρ-cresol and formaldehyde, poly (ρ-hydroxystyrene) * poly (P-hydroxy-α-methylbenzene Ethylene), copolymers of P-hydroxystyrene or P-hydroxy-α-methylstyrene with ethoxylated styrene or acrylic acid and / or methacrylic acid and (meth) acrylates, It is used in a conventional manner with dihydrofuran, 3.4-dihydropyran * benzyl halides, alkyl halides, haloacetic acid, haloacetates, atmospheric carbonates, alkylsulfonyl Halides, aromatic sulfonyl halides, dialkyl dicarbonates or trialkylsilyl halides are reacted. Also suitable are polymers of the type P_ (2-tetrahydropiperyl) monooxystyrene or P- (third_butyloxycarbonyl) monooxystyrene with (meth) acrylic acid * (methyl ) -50- This paper size is applicable to China Solid State Standard (CNS) Α4 size (2 丨〇X297mm) ------------ ^ ------ ΐτ ----- -^ (Please read the note on the back before filling out this page) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7__ V. Description of the Invention (《2) Acrylic acid esters and / or P-ethenyl Polymers of styrene and polymers of p-hydroxystyrene and / or P_ (2-tetrahydropyranyl) monooxystyrene and 3-hydroxybenzyl (meth) acrylates, if necessary It can be additionally protected by reacting with the compounds listed above. Particularly suitable are polymers that are transparent in the wavelength range from 180 to 1000 micrometers and carry two bases that cause solubility changes after acid-catalytic deprotection, and increase the dissolution of acid producers Water-repellent and hydrophilic base plaques that ensure the developability of water-borne properties. Examples of such polymers are acrylates and methacrylates, which are prepared from the corresponding monomers via co- or tri-polymerization. Such monomers can also carry organosilicon radicals, for example, to increase resistance in dry etching methods. Examples of monomers are: methyl (meth) acrylate, (meth) acrylic acid, tertiary butyl (meth) acrylate, trimethylsilyl methyl (meth) acrylate * 3-oxycyclohexyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, adamantane (meth) acrylate, cyclohexyl (meth) acrylate, norberyl (meth) acrylate (Norbornyl) ester. The present invention accordingly also relates to a chemical effect-enhancing positive-acting anti-resistance substance, which includes a compound of formula I, 13 or 11) as a provider of a photosensitive acid. Particularly preferred is a chemically effective positive amplifying substance including a compound of formula lb as a provider of a photosensitive acid. -5 1- This paper uses China National Standard (CNS) A4 specifications (210X297 mm) — III ——— — — — Gutter (please read the notes on the back before filling this page) Central Bureau of Standards, Ministry of Economic Affairs Consumption cooperation with employees Du printed A7 B7_ V. Description of the invention (#) The present invention is also related to a photoresist substance, which includes polymers that are transparent in the wavelength range of 180 micrometers. Specific specific facts about sexually resistive substances include a thin layer-forming polymer from 75 to 99.5 weight percent, which includes protective groups that can be removed via acid catalysis * and from 0.5 to 25 weight percent The oxime sulfonates of formula I, la or lb, percentages are based on the solids content of the composition. In this regard, the preferred composition includes the polymers described above in weight percentages from 80 to 93 and weight percentages from 1 Oxime sulfonic acid to 20. Another specific matter is a positive impedance material, which includes an acid-inert thin layer-forming polymer from 40 to 90 weight percent as an adhesive, and from 5 to 40 weight percent. One Monomeric or polymerizable compounds having protective groups that can be removed by acid catalysis, and oxime sulfonates of formula I, la or lb in weight percentages from 0.5 to 25, the percentages are relative Calendar in the composition. Preferred among these compositions are acid-inert adhesives ranging from 50 to 85 percent by weight, monomeric or polymeric solubilizing inhibitors ranging from 10 to 30 percent by weight, and The oxime monosulfonates from 1 to 15 weight percent. The oxime sulfonates can also act as photo-activatable solubility promoters. In this case, the compound is added to a thin layer-forming material, Original -52- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 male) --------- Γ installed ------ order ------ line (please Please read the notes on the back before filling in this page) Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs «. A7 £ 7_ V. Description of Invention (j) 霣 does not include heating or κ dynamic radiation when irradiating with oxime The sulfonate polymerized ingredients. However, the oxime sulfonate reduces the thin layer-forming material to dissolve in a suitable developer The speed of the intermediary value. This promotion effect can be offset by irradiating the mixture with the kinematic radiation, so a positive image can be produced. This application is described in, for example, ΕΡ-Α- 241 4 2 3 〇 Finally, a further particularly specific fact of the present invention is a positive impedance material, which includes a compound of formula 1, la or lb and an adhesive, which is essentially insoluble in an alkaline developer and is in formula 1, La or lb compounds become soluble in the presence of photolysis products. In this case, the oxime sulfonate compounds already mentioned are usually from 5 to 50% by weight, based on the solid content of the composition . The oxime sulfonate according to the present invention is used in a chemical effect amplifying system, which operates based on the principle of removing a protective group from a polymer, and generally generates a positive impedance. Positive impedances are preferred to negative impedances in many respects, especially because of their better resolution. However, the use of a positive impedance material mechanism is also beneficial for producing negative images in order to integrate the advantages of the high resolution of the positive impedance material and the characteristics of the negative impedance material, which can be achieved by introducing a so-called image-flip step, which step See, for example, EP-A-361 906. For this purpose, the impedance material material for image-by-image radiation will be subjected to image-by-image radiation before the development step, for example, a gas-5 3-This paper size is applicable to China National Standard (CNS) Α4 specification (210 × 297 mm), »*- ------------- ^. 1 Gen ------______ Spring (Please read the notes on the back before filling this page) System A7 £ 7_ 5. Description of the invention (p) Physical examination will be processed so that the produced acid can be neutralized. Subsequently, a second epitaxy and thermal post-processing are performed over the entire area and the negative image is developed in the usual manner. In addition to the components already described, the negative and positive photoresist composition compositions may additionally include one or more additives commonly used in photoresists, and their components are familiar to those skilled in the art, For example, fluidity improvers, wet liquefiers, adhesives, thixotropic agents, colorants, pigments * fillers, solubility accelerators, and the like. The reaction can be accelerated by the addition of photosensitizers, which can move and / or broaden the sensitivity of the optical frequency, especially aromatic carbonyl compounds such as benzophenone, thioflavones, and 3-Methyl coumarin derivatives and 3- (arylmethylidene) sialazolinium, but can also be eosin, rhodanine, and erythrosine For application, the composition class must include a solvent. Examples of suitable solvents are ethyl acetate, 3-methoxymethyl propionate, ethyl propionate, 2-heptane, dimethyl ether dimethyl ether, cyclopentane, cyclohexyl Hexanone, 7-butyrolactone, ethylmethylphosphonium, 2-ethoxyethanol, 2-ethoxyethyl acetate and especially 1-methoxy-2-propyl acetate. The solvent may also be in the form of a mixture, such as two or more of the aforementioned solvents. The choice of the solvent and its concentration depends, for example, on the characteristics of the composition and the coating method. -54- This paper size is applicable to China National Mou (CNS) A4 specification (210X297 mm) ----------- Loading ------ 1T ------ ^ (please first Read the notes on the back and fill in this. I) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. A7 B7. 5. Description of the invention. Ti) Use the conventional coating method to uniformly drag the solution onto the substrate. For example, spin-coating. Coating, dip coating, knife coating, curtain coating, brushing * spray coating, and reverse roll coating. It is also possible to apply the photosensitive layer to a temporary elastic support and then transfer the final substrate (layering) by layer-by-layer transfer. The amount of application (layer thickness) and characteristics of the substrate (coated substrate) vary depending on the intended application. The coating thickness is typically about 0.1 micrometers to 100 micrometers K. The composition of the present invention can be used as an electronic photoresist, such as an etching resistor, a plating resistor, and a solder resistor, to prepare an integrated circuit or a thin-film transistor-resistor; TFT-resistor; and to prepare a printed board such as an adhesive Offset printing or screen printing, used for etching of moldings or lithographic lithography. The range of coating substrates and processing conditions is therefore quite wide. The composition of the present invention is a coating substrate that is also particularly suitable as a substrate of all types, such as wood, wood, paper, ceramics, glass, plastic, such as polyester, polyethylene terephthalate, and polyolefin. Acetate or stigmatol acetate, especially in film form, also includes metals such as nickel, iron, zinc, magnesium or cobalt, or especially copper and aluminum, also silicon or silicon dioxide or silicon nitrite, on a substrate Images are formed by image-wise exposure. After the coating operation, the solvent is usually removed by heating, and a layer of photoresist is obtained on the substrate. The drying temperature must be lower than -55 in the resistive substance. This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) I Binding — III line (Please read the precautions on the back before filling this page) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. The invention shows the temperature at which the ingredients may be heated. Therefore, κ must be handled with care, especially in the case of negative photoresist 霣. In general, the drying temperature should not exceed 80 to 130t: 〇 The impedance and the coating are subsequently irradiated image by image. The proper term " imagewise radiation " contains K-kinetic radiation for a predetermined form of radiation, that is, development through a photomask containing a predetermined form, such as a slide * M and use, for example, via The computer-controlled laser light source moves on the surface of the coated substrate to generate an image. After exposure and, if necessary, heat treatment, use the developer in the unexposed areas of the photoresist (in the case of a positive photoresist substance) or in the irradiated area (in the case of a negative photoresist substance) It is removed by a method known per se. It usually takes time before the development step to allow the acid-sensitive component of the resistive substance composition to react. In order to accelerate the reaction and thus develop a sufficiently different solubility between the irradiated and non-irradiated areas of the resist coating in the developer, the coating is preferably heated before development. Heating can also be performed or started during irradiation. Preference is given to temperatures from 60 to 150 ° C. The length of time depends on the heating method, if necessary * The most suitable period can be easily determined by the skilled person through some routine experiments. Usually from seconds to minutes. For example, using heating-56- this paper size uses Chinese National Standard (CNS) A4 specifications (210 > < 297 mm) --------- ΗII (please read the note on the back first) (Fill in this page again.) Order A7 B7 Imprint of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of invention (D) 1 1 I. The period from white 1 () to 300 seconds is very suitable; traditional roasting is used. 1 1 1 case * 1 to 30 minutes is very suitable. Very important / — ν 1 I Please 1 1 is the non-radiated position of t on the resistive substance according to the present invention. Read I I Read 1 The latent acid supplier needs to be stable under these processing conditions. Note 1 of 1 Note | It means that the covering material is developed later. The position of the covering material after irradiation is more easily dissolved and removed in the developing matter 1 I and 1 I / agent. If necessary, shake the work item slightly. 4 books I! Equipment »Lightly brush the coating in the developer bath or spray-type development can accelerate the processing of the sheet 1 I Step 〇 Water-based sickle development commonly used in impedance material technology Agents such as 1 1 I * can be used for development. Such developers include, for example, sodium hydroxide or hydrogen 1 1 corresponding to potassium oxide, carbonates, silicates, or silicates. Order silicic acid but prefer metal-free bases, such as ammonia or amines, such as ethyl 1 I amine propyl propyl amine diethyl amine di 1 propyl amine triethyl amine 1 I 9 methyl Diethylammonium amines, such as dimethylacetamide, triethylenzyme1 1 Amine quaternary hydroxides, such as tetramethylammonium hydroxide or tetraethylammonium hydroxide 0 Developer solubilizers usually reach 0.5 N but often diluted in a suitable 1 I manner. For example, about 0.1 Ν solution is 1 I suitable 0. The choice of developer depends on the characteristics of the light-curable surface coating, and 1 1 1 9 especially depending on the adhesive used or the light obtained. The speciality of the decomposition product is 1 1 set 0. Aqueous developer solubilizers | If necessary, it also includes a relatively small amount of wet 1 1 moisturizers and / or organic solvents. The typical type I organic solvents that can be added to the developer liquid are f. For example, cyclohexanone 9 2- -ethoxyacetic acid | methyl 1 1 I benzene, acetone f isopropylase, and two of these solvents A mixture of one or more types 1 1 -57-1 1 This paper size is applicable to China National Standards (CNS) 8 4 grids (210X297 mm) Printed by the Consumers' Cooperatives of the China National Standards Bureau of the Ministry of Economic Affairs A7 B7 5. Description of the invention (0) The class. A typical aqueous / organic developer system is based on Butylcellosolve® / water. It is known from EP — A — 5 9 2 1 3 9 that oxime sulfonates can be used as light-activatable acid generators in compositions suitable for surface treatment and cleaning of glass, aluminum and starved surfaces. class. The use of these compounds in this fluorinated silane system results in compositions having significantly better storage characteristics than those using taurate. When used in combination with a coloring agent that changes color at a change in pH, oxime sulfonates can also be used to print-out " images, as described in Japanese Patent Application JP-A Hei 4 3 2 8 5 5 2 or US-A-5 2 3 7 059. This color-shift system according to EP-A-199 672 can also be used to monitor goods that are sensitive to heat or radiation. In addition to the change in color M, pigment crystal precipitation may occur during the acid-catalytic deprotection of soluble pigment molecules; this can be used to produce color filters. Suitable cross-linked junctions include compounds of formula I, la or lb. The radiation source of the composition is a wavelength from about 180 to 1000, such as from 300 to 600, or preferably from 380 to 600, such as from 380 to 600 micrometers. Which emits radiation. Point light sources and flat radiators (light felts) are suitable. Implementation -58- This paper size is in accordance with Chinese Standard (CNS) A4 specification (210X297mm)! II _ | Binding III Order — I —— i II Line (Please read the precautions on the back before filling this page) Printed by the Central Bureau of Standards of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, A7 B7_ V. Description of the invention (<) Examples are carbon arc lamps, xenon arc lamps, medium pressure, high pressure and low pressure mercury lamps. Samarium halides (gold halide lamps), microwave-irritating metal vapor lamps, laser lamps, superactinic fluorescent tubes, fluorescent lamps, incandescent cyan lamps, electric flashing lamps, Photographic flood lamps, electron beams and X-rays are manufactured via synchrotron radiation, or laser plasma. The distance between the lamp and the substrate to be covered in the present invention may vary depending on the application and the type and / or power of the lamp, such as between 2 cm and 15 (] cm. Particularly suitable It is a laser light source, such as a laser laser, such as a Krypton F laser for 248 micrometers of wavelength or an Ar-F laser for 193 micrometers of wavelength. It can also be used in the visible light range or red light range. The most suitable is the radiation of the mercury h and g bands at the wavelengths of 4 3 6 and 4Q5 micro millimeters. Suitable light sources are therefore especially mercury vapor lamps, especially medium and high pressure mercury lamps. The emission bands of other wavelengths of this radiation can be Eliminate it according to your preferences, especially when using short wavelengths of Pedang. The distance between the lamp and the work object, for example, can be from 2 cm to 150 cm, depending on the intended use and type and / or intensity of the lamp However, it is also possible to use a low-energy lamp (such as a fluorescent tube) • It can radiate in a suitable wavelength range, an example is the Philips TL03 lamp. A suitable laser-beam source is, for example, an argon ion laser Shoot Wavelengths of 454, 458, 466, 472, 478, and 488 μm. Also suitable are, for example, a helium / cadmium laser that emits 442 μm of radiation or a laser that emits in the UV range. Use this class When irradiating, it is not necessary to use a photomask in contact with the photopolymerizable coating. -59- This paper size is applicable to China National Standard (CNS) A4 (210X297 mm). ------ Order ------ line (please read the notes on the back before filling out this page) The consumer cooperation of the Central Standards Bureau of the Ministry of Economy Du printed Α7 Β7 V. Description of invention (rt) Positive or negative impedance; the controlled laser beam can be written directly on the covering. For this purpose, the high sensitivity of the materials according to the invention is very advantageous, so that at relatively low intensity There is a high writing speed. During the irradiation, the oxime sulfonate in the composition in the surface-covered and irradiated area is decomposed to form sulfonic acid. In contrast to the conventional high-intensity radiation for UV curing, the use of radical The compounds of the present invention can be activated under relatively low intensity radiation. Such radiation includes, for example, sunlight (sunlight), and a radiation source equivalent to sunlight. The spectral composition and intensity of sunlight are different from those of artificial radiation sources used in V curing. Compounds according to the present invention The absorption characteristics are particularly suitable for the use of sunlight as a natural source of radiation required for maturation. A daylight equivalent artificial light source that can be used to activate the compounds according to the invention is understood to be a low intensity emitter, such as some fluorescent lamps such as Philips TL05 Special Fluorescent Lamp or Philips TLO 9 Special Fluorescent Lamp. Deng or Sunlight with high daylight content can particularly satisfactorily cure a surface-coating surface in a non-nailed manner. In this case, an expensive curing apparatus is redundant and the composition can be particularly used for externally complete curing of M daylight or a daylight-equivalent light source, which is an energy saving method and prevents volatile organics used in external applications. Divergence of sexual components. Contrary to the method of conveyor belts suitable for flat elements, * sun curing can also be used for static or fixed objects and structures. -6 0-This paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) (Please read the precautions on the back before filling this page) Printed by the Consumers Cooperative of the Bureau of Standards and Loss Standards, Ministry of Economic Affairs 2. Description of the invention The surface coating to be heated can be directly exposed to a light source equivalent to sunlight or sunlight. However, * heating can also occur behind a transparent layer (such as a glass panel or a plastic sheet). The compounds of the formulae I, la and lb are usually added to the photo-activatable composition in an amount of from 0.1 to 30% by weight, such as from 0.5 to 10% by weight, especially from 1 to 5% by weight. The present invention also relates to compounds of the formulae I, la and lb, which are used in the production of surface coatings, printing inks, printing plates, dental compositions, color filters, impedance materials or image recording properties. In the case of materials or image recording materials for recording full-image imaging, as a photosensitive acid provider, M provides radiation having a wavelength exceeding 390 millimeters. The following examples further illustrate the invention. In the following description and patent application, unless otherwise stated, parts or percentages are based on weight. Example 1: ct_ (methylphenylsulfonyloxyimino)-3,4-dimethoxybenzyl cyanide 1.1 α-hydroxyimino-3,4-dimethoxybenzyl物 -6 1- The paper Λ degree applies to China National Standard (CNS) Α4 specification (210X297 mm) I -------- ^ 1 —------ 1T ------. ^ (Please read the note on the back before filling in this page) A7 B7___ printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of invention (L ^ f) 47 g (1.17 mol) of NaOΗ, which was dissolved in In 450 ml of formazan, 208.03 g (1.17 mol) of 3,4-dimethoxybenzyl gaseous substance in a conical flask for sulfonation was added and the solution was cooled in an ice-bath to 0—5Ό. After stirring at this temperature for 4 hours, 1.17 moles of Zhao-like methyl nitrite (via 38 liters of 沣 Hz S04) was dissolved in 82 ml of water and added to 97.1 grams of

NaN02於 59毫升之水及62毫升之甲酵中所形成的溶液内而予 K 當場製備，見 Org. Synthesis 59， 95， 1979 )被導人該溶疲中。該反懕溶疲随後進行攪拌一整夜且之後將氮通入該溶液中。將甲酵為於一旋轉性揮發器中蒸餾去除且該棕色殘餘物於一甲苯及水的混合物中攪拌 30分鐘而製成泥狀。將諸相分離並將'水性相Μ甲苯進行清洗並K濃 HC1調成酸性。產物Κ一棰灰褐色沉澱物的形式得到。將沉澱物濾除， Μ水清洗成中性，於真空狀態下進行乾燥且随後自乙酸乙酯中進行再结晶。11 4公克（4 7% )之α -羥基亞胺基— 3，4一二甲氧基苄基氰化物Μ灰褐色固體的形式得到，其具有熔點183- 191C。元素分析：C i 〇 H i 0 N2 〇3 ( 2 0 6 . 2 0 ) C [%} Η [% ] Ν [96 ] -62- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ----------^------tr------m (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標隼局貝工消費合作社印裝 A7 ___B7 五、發明説明（^) 計算值： 58.25 4.89 13.59 發現值： 58.22 4.97 13.54 1 -2 ： α - (4 一甲棊苯基磺藤碁氣亞胺基）一 3，4 — 二甲氧基苄基氰化物 51.6 公克（0.25莫耳）之α —羥基亞胺基一 3，4-二甲氧基苄基氰化物及 30Q 奄升之三乙基一胺被溶解於 300奄升之THF中並於一冰浴中進行冷卻至0— 5·〇。Μ — 小時的時間逐滴將 52.4公克（0.275莫耳）之對—甲苯磺酸氛化物於 65奄升之THF中所形成的溶液加入該溶液中。经過3 小時Κ後*將該冰浴移除且將該反應混合物於室溫進行搅拌一整夜。隨後加入 150牽升之CH2 Cl2 ，已沉澱的銨鹽被濾出且將濾液經由重覆Μ水及稀釋HC1進行清喜來去除過量的三乙基胺。經過在硫酸镁上進行乾燥Μ 後，將溶劑為於一旋轉性揮發器中蒸餾去除且將刺下的殘餘物自甲苯中進行再结晶。80.8公克（90% )之α — （ 4 一甲基苯基磺醢基氧亞胺基）_3，4一二甲氧基苄基氰化物以淡黃色结晶的形式得到，其具有熔點1 6 1 - 1 6 3 υ。化合物之1 H— NMR光譜顯示其為一種純化的立體異構物。該物質的UV光譜（乙腈）顯示一廣泛的吸收帶，最大在350 微毫米（ε = 1134Q)，其延伸至 435微毫米。 -63- 本纸張尺度適用中國國家標準（CNS ) Α4規格（2丨0X297公釐） (請先閲讀背面之注意事項再填寫本頁訂線經濟部中央標準局員工消费合作社印製 A7 £7_ 五、發明説明% 6) 元素分析：C ! 7 H i s N2 Os S ( 3 6 0 . 38)NaN02 was prepared on the spot in a solution of 59 ml of water and 62 ml of formazan, see Org. Synthesis 59, 95, 1979). The reaction was then stirred overnight and thereafter nitrogen was passed into the solution. The formazan was distilled off in a rotary volatilizer and the brown residue was stirred in a mixture of toluene and water for 30 minutes to make a mud. The phases were separated and the 'aqueous phase M toluene was washed and K concentrated HC1 was made acidic. The product K was obtained as a beige precipitate. The precipitate was filtered off, washed with M water to neutrality, dried under vacuum and subsequently recrystallized from ethyl acetate. 11 4 g (4 7%) of α-hydroxyimino-3,4-dimethoxybenzyl cyanide M was obtained in the form of a beige solid having a melting point of 183-191C. Elemental analysis: C i 〇H i 0 N2 〇3 (2 0 6. 2 0) C [%} Η [%] Ν [96] -62- This paper size applies to China National Standard (CNS) A4 (210X297) Li) ---------- ^ ------ tr ------ m (Please read the notes on the back before filling this page) Printed A7 ___B7 V. Description of the invention (^) Calculated value: 58.25 4.89 13.59 Found value: 58.22 4.97 13.54 1 -2: α-(4 methylaphenylphenylsulfonium imidate)-3, 4-2 51.6 g (0.25 mol) of methoxybenzyl cyanide α-hydroxyimino- 3,4-dimethoxybenzyl cyanide and 30Q liter of triethylmonoamine were dissolved in 300 liter In THF and cooled in an ice bath to 0-5.0. A solution of 52.4 grams (0.275 moles) of p-toluenesulfonic acid in 65 liters of THF was added dropwise to the solution over a period of M hours. After 3 hours, the ice bath was removed and the reaction mixture was stirred at room temperature overnight. Subsequently, 150 liters of CH2Cl2 was added, the precipitated ammonium salt was filtered off, and the filtrate was purified by repeating M water and diluting HC1 to remove excess triethylamine. After drying on magnesium sulfate, the solvent was distilled off in a rotary volatilizer and the residue from the thorn was recrystallized from toluene. 80.8 g (90%) of α- (4-methylphenylsulfonyloxyimino) -3,4-dimethoxybenzyl cyanide is obtained in the form of pale yellow crystals, which has a melting point of 1 6 1 -1 6 3 υ. The 1 H-NMR spectrum of the compound showed that it was a purified stereoisomer. The substance's UV spectrum (acetonitrile) shows a broad absorption band, with a maximum of 350 μm (ε = 1134Q), which extends to 435 μm. -63- This paper size applies to Chinese National Standard (CNS) Α4 size (2 丨 0X297 mm) (Please read the precautions on the back before filling out this page. Threading A7 printed by the Central Consumer Bureau of the Ministry of Economic Affairs Consumer Cooperatives V. Description of the invention% 6) Elemental analysis: C! 7 H is N2 Os S (3 6 0. 38)

Cm H {%} N [%] S {%] 計算值：56.6 6 4.4 8 7.7 7 8.9 0 發現值：56.76 4.55 7.71 8.89 實施例2: α — （4 一甲基磺醯基氧亞胺基）一 3，4一二甲氧基苄基氰化物如1.2.所述，14.4公克（0.07莫耳）之c(一羥基亞胺基一 3，4一二甲氧基苄基氰化物與8.8公克（0.077莫耳）之甲烷磺醯氛於三乙基胺的存在下進行反應。該反應混合物的GC分析顯示兩種異構物類的混合物的形成比例為 3 : 1。自乙酸乙酯中進行再结晶後，1 2 . 0公克（6 0% ) 之α — （4 一甲基磺醢基氧亞胺基）_3，4—二甲氧基苄基氮化物Μ —黃色粉末的形式得到，其具有熔點14Q — 。1 H— NHR光譜顯示混合物中（Ε)及（Ζ)異構物類以8 :2的比例存在。該異構性混合物顯示一 UV/ Vis光譜（乙膈）在 3 0 0微毫米（ε= 8 4 0 0 )及 3 3 7微毫米（ε = 1033Q)，其延伸至43Q微毫米，具有兩個吸收帶。元素分析：C i i Η! 2 N2 0S S ( 2 8 4.2 9) -64- 本紙張^度適用中國國家揉準（CNS ) Α4«Μβ· ( 210X297公釐） --------------ΐτ------.^ (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消费合作社印製 A7 B7 五、發明説明（έί ) cm Η [%] Ν [X] S [%] 計算值： 46.47 4.25 9.85 11.28 發現值： 46.66 4.32 9 . 87 11.45 經由將產物混合物進行快速色層分析（矽膠，洗提劑 :石油醚/乙酸乙酯 2:1) ，（Z)異構物可以純化的形式得到，其為黃色固體而具有熔點152 — 158C。實施例 3 : α — （ 4—甲基苯基磺醢基氧亞胺基）一 4 一硫甲基苄基氰化物 3.1 ： 4 —硫甲基一苄基酵甲烷磺酸酯於一磺化用錐形瓶中，50公克（0.32莫耳）之4-甲基硫苄基酵及46.3 公克（0.32莫耳）之甲基磺醢氯被溶解於 250 毫升之甲苯中且，在10¾進行冷卻，將32 . 5 公克（0.32莫耳）之三乙基胺逐滴加入。該反應混合物隨後被加熱至室溫並進行攪拌一整夜。隨後將 400 毫升之 2N氫氛酸緩慢加入該反應溶疲中並加Μ攪拌。將諸相分離且有機相以水加Κ濟洗，進行於Mg S04上進行乾燥並於一旋轉性揮發器中進行濃縮。60公克（80%)之4 —甲基硫苄基酵甲垸磺酸酯以一黃色油狀物的形式得到。 -65- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） --------,丨裝------訂------線 (請先閲讀背面之注意事項再填寫本頁) 經濟部中夬標準局貝工消费合作社印製 Α7 Β7 五、發明説明（ 3.2 : 4 —甲基硫苄基腈 92.4公克（0.4莫耳）之4一甲基硫苄基醇甲烷確酸酯於室溫下加入31.6 公克（0.64莫耳）之氰化納於300 奄升之二甲基亞礓中所形成的溶液内且該溶液於室溫下進行授拌一整夜。將該溶液随後倒入冰一水中並將得到的固髖被濾出。將產物自異丙酵/水（1:1)中進行再结晶。 56公克（87%)之4_甲基硫苄基腈以無色固體的形式得到，其具有熔點4 4 - 4 4 · 5 C。 3.3: ct —羥基亞胺基一 4 一甲基硫苄基氰化物 10公克（0.06莫耳）之甲基硫苄基腈為如1.1所述與 0. (3 6莫耳之亞硝酸甲酯進行反應。反應完成後，4.2公克（3 6%)之α—羥基亞胺基—4—甲基硫苄基氰化物Μ淡黃色粉末的形式得到，其具有熔點132 - 133C。 3 . 4 : α - ( 4—甲基苯基磺醢基氧亞胺基）一 4 一硫甲基苄基氰化物 4公克（0.021冥耳）之羥基亞胺基一 4 一甲基硫苄基氰化物在25 毫升之 THF中如1.2所述，在3.16公克（ 0.031 莫耳）之三乙基胺的存在下，與 4.35 公克之（ -66- 本紙張尺度適用中國國家樣準（CNS ) Α4規格（210Χ297公釐） ---------/—装------1Τ------^ (請先閲讀背面之注意事項再填寫本頁) 經濟部中央榡準局貝工消#合作社印装 A7 _____B7__ 五、發明説明（^)) 0 . 0 2 3 冥耳）之對一甲苯磺酸氰化物進行反應。在反應完成之後，6.25公克（87%)之粗製產物以淡棕色固趙的形式得到•該固體自乙酸乙酯中進行再结晶而得到3 . 8公克之α — （4 一甲基苯基磺醢基氧亞胺基）—4一硫甲基苄基氰化物，其為淡黃色固體形式而具有熔點102 — 107*C。1 H- NMR 光譜顯示（Z)及（E)異溝物的混合物之存在。 UV/ Vis光譜顯示在 348微毫米（ε = 1 880 0)，其延伸至 440微毫米，有一吸收帶。元素分析：C: s Hi 4 Nz 〇3 S2 ( 346.4) cm Η [%) Ν {%] S {%] 計算值 55.48 4.07 8.09 18 .51 發現值 55.33 4.09 7 . 87 18 .75 實施例4: α - （4 一十二垸基苯基磺醢基氧亞胺基）一 3，4一二甲氧基苄基氰化物類似於實施例1的製備方法，14.4公克（0.07莫耳 )之α —羥基亞胺基一 3，4 一二甲氧基苄基氰化物在室溫與 26.56公克（9.077莫耳）之4 —十二烷基苯磺醢氯在 100 毫升之四氫呋喃中在10.6公克（Q.105莫耳）之三乙基胺的存在下進行反應。為了完成反應，該反應混合物 -67- 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐） ---------------IT------漆 (請先閱讀背面之注意事項再填寫本頁) A7 B7Cm H {%} N [%] S {%] Calculated value: 56.6 6 4.4 8 7.7 7 8.9 0 Found value: 56.76 4.55 7.71 8.89 Example 2: α — (4 monomethylsulfonyloxyimino group) A 3,4-dimethoxybenzyl cyanide as described in 1.2. 14.4 grams (0.07 moles) of c (monohydroxyimino-3,4-dimethoxybenzyl cyanide with 8.8 grams (0.077 mol) of methanesulfonium was reacted in the presence of triethylamine. GC analysis of the reaction mixture showed that the ratio of the formation of a mixture of two isomers was 3: 1. After recrystallization, 12.0 g (60%) of α- (4-monomethylsulfonyloxyimino) -3,4-dimethoxybenzyl nitride M-yellow powder was obtained, It has a melting point of 14Q — .1 H — NHR spectrum shows that (E) and (Z) isomers in the mixture exist in a ratio of 8: 2. The isomeric mixture shows a UV / Vis spectrum (acetamidine) at 3 0 0 micromm (ε = 8 4 0 0) and 3 3 7 micromm (ε = 1033Q), which extends to 43Q micromm and has two absorption bands. Elemental analysis: C ii Η! 2 N2 0S S (2 8 4.2 9) -6 4- This paper is suitable for China National Standards (CNS) Α4 «Μβ · (210X297 mm) -------------- ΐτ ------. ^ (Please read first Note on the back, please fill out this page again) Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (（ί) cm έ [%] Ν [X] S [%] Calculated Value: 46.47 4.25 9.85 11.28 Found Value : 46.66 4.32 9. 87 11.45 After rapid chromatography of the product mixture (silica gel, eluent: petroleum ether / ethyl acetate 2: 1), the (Z) isomer can be obtained in purified form as a yellow solid And it has a melting point of 152-158C. Example 3: α- (4-methylphenylsulfonyloxyimino) -4-thiomethylbenzyl cyanide 3.1: 4-thiomethyl-benzyl ferment methane In a conical flask for sulfonation, 50 g (0.32 mol) of 4-methylthiobenzyl ferment and 46.3 g (0.32 mol) of methylsulfonium chloride were dissolved in 250 ml of toluene Neutralize, cool at 10¾, add 32.5 grams (0.32 moles) of triethylamine dropwise. The reaction mixture is then heated to room temperature and stirred for one minute. Overnight. Then 400 ml of 2N aqueous hydrochloric acid atmosphere was slowly added to the reaction solution and added Μ stirred fatigue. The phases were separated and the organic phase was washed with water plus K, dried over Mg S04 and concentrated in a rotary volatilizer. 60 g (80%) of 4-methylthiobenzyl mesylate was obtained as a yellow oil. -65- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) --------, 丨 installed ------ order ------ line (please read the back first Please pay attention to this page, please fill in this page) Printed by the China Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, A7, B7 V. Description of the invention Benzyl alcohol methane ester was added to a solution of 31.6 g (0.64 mol) of sodium cyanide in 300 liters of dimethyl sulfene at room temperature, and the solution was stirred at room temperature. Overnight. The solution was then poured into ice-water and the resulting solid hip was filtered off. The product was recrystallized from isopropion / water (1: 1). 56 g (87%) of 4_ Methylthiobenzyl nitrile is obtained as a colorless solid with a melting point of 4 4-4 4 · 5 C. 3.3: ct —hydroxyimino-4 4-methylthiobenzyl cyanide 10 g (0.06 mol) The methylthiobenzylnitrile was reacted with 0.3 (36 moles of methyl nitrite) as described in 1.1. After the reaction was completed, 4.2 g (3 6%) of α-hydroxyimino-4-methyl Thiothiobenzyl cyanide M Obtained as a yellow powder with a melting point of 132-133C. 3.4: α-(4-methylphenylsulfonyloxyimino) -4 monothiomethylbenzyl cyanide 4 g (0.021 ) Hydroxyimino-4 monomethylthiobenzyl cyanide in 25 ml of THF as described in 1.2 in the presence of 3.16 g (0.031 mol) of triethylamine and 4.35 g of (- 66- This paper size is applicable to China National Standard (CNS) Α4 specification (210 × 297 mm) --------- /-installation ------ 1T ------ ^ (Please read first Note on the back, please fill in this page again)) The Central Government of the Ministry of Economic Affairs, Central Bureau of Standardization, Bei Gong Xiao #Cooperative Society Printing A7 _____B7__ V. Description of the Invention (^)) 0. 0 2 3 Mullion) Reaction of Monotoluenesulfonic Acid Cyanide After the reaction was completed, 6.25 g (87%) of the crude product was obtained as a light brown solid. This solid was recrystallized from ethyl acetate to obtain 3.8 g of α- (4-methylphenyl). Sulfonyloxyimino) -4-thiomethylbenzyl cyanide, which is a light yellow solid with a melting point of 102-107 * C. 1 H-NMR spectrum shows (Z) and (E) The existence of a mixture of heterodyne. UV / Vis spectrum shows at 348 micrometers (ε = 1 8880), which extends to 440 micrometers and has an absorption band. Elemental analysis: C: s Hi 4 Nz 〇3 S2 (346.4) cm Η (%) Ν {%] S {%] Calculated 55.48 4.07 8.09 18 .51 Found 55.33 4.09 7. 87 18 .75 Example 4: α-(4 dodecyl phenyl Sulfonyloxyimino group) A 3,4-dimethoxybenzyl cyanide is similar to the preparation method of Example 1. 14.4 g (0.07 mol) of α-hydroxyimino group 3,4 one two Methoxybenzyl cyanide at room temperature with 26.56 g (9.077 mol) of 4-dodecylbenzenesulfonyl chloride in 100 ml of tetrahydrofuran at 10.6 g (Q.105 mol) of triethylamine The reaction is performed in the presence of. In order to complete the reaction, the reaction mixture -67- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) --------------- IT ------ lacquer (Please read the notes on the back before filling this page) A7 B7

兀素分析： C2 8 H3 8尺2 〇5 S c C % ] Η [ % ] Ν [ % 3 S 〔％〕計算值： 65.34 7.44 5.44 6.23 發現值： 64.87 7.36 5.49 6.14 實施例5 : 〇t - （ 2—丙基磺醯基氧亞胺基）二甲氧基苄基氰化物如1.2所述， 16.5公克（0.08莫耳）之α -羥基亞胺基_3，4 —二甲氧基苄基氰化物與12.6公克（0·088冥耳）之 2—丙烷磺醢基氯化物在三乙基胺的存在下進行反懕。粗製產物自乙酸乙酯/己烷進行再结晶得到 2 1 · 9公 -68* 本紙張尺度適用中國國家榇华（CNS ) A4g格（210Χ2Ή公釐） ^1.^1 In -1-!*= I- -1« nn ml m· InTJ 03 言 (請先閱讀背面之注意事項再填寫本頁) Μ Β7 五、發明説明qc) 克（88%)之α - (2 —丙基磺醯基氧亞胺基）—3，4 —二甲氧基苄基氣化物，其為灰揭色結晶而具有熔點 90.5 -93.5°C。化合物之1 H-NMR光譜顯示其為純化的立體異構物。該物質的 UV光譜（乙腈）顯示一廣泛的吸收帶，其最大值在 346微毫米（ε= 1 1 6 5 0 3 4 )，其延伸至434微毫米。元素分析：C i 3 H i s 0S S (312.34) C [%] Η [%] Ν [%] 計算值： 49.99 5.16 8.97 發現值： 50.07 5.26 8.88 S施例S: ct — (2，4，6-參（異丙基）苯基磺醯基氧亞胺基）_3，4 一二甲氧基苄基氟化物如1 . 2所述，8 . 2 5公克（0 . 0 4莫耳）之α -羥基亞經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 胺基一3，4一二甲氧基苄基氰ib物與13.3公克（0.044冥耳）之 2，4* 6—參（異丙基）苯磺騸氯在三乙基胺的存在下進行反懕。粗製產物自乙酸乙酯/己烷中進行再结晶後， 14.25公克（75%)之《 - (2，4，6 —參（異丙基 )苯基磺醯基一氧亞胺基）_3，4 一二甲氧基一苄基氰化物Μ灰褐色结晶的形式得到，其具有熔點 9 0 . 5 - 9 3 . 5 TC。 -69- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐）經濟部中央標準局貝工消费合作社印製 A7 ___B7__ 五、發明説明該化合物之1 H- NMR光譜顯示其為一純化的立體異構物。該物質的UV光譜（乙腈）顯示一廣泛的吸收帶，其最大值在 3 52微奄米（e = 1 1 0 0 0)，其延伸至 4 3 3微毫米。元素分析：C2 5 H3 2 N2 Os S ( 4 7 2 . 6)Element analysis: C2 8 H3 8 feet 2 〇5 S c C%] Η [%] Ν [% 3 S 〔%] Calculated value: 65.34 7.44 5.44 6.23 Found value: 64.87 7.36 5.49 6.14 Example 5: 〇 t- (2-propylsulfonyloxyimino) Dimethoxybenzyl cyanide As described in 1.2, 16.5 g (0.08 mole) of α-hydroxyimido-3,4-dimethoxybenzyl The cyanide was reacted with 12.6 g (0.088 gram) of 2-propanesulfonyl chloride in the presence of triethylamine. The crude product was recrystallized from ethyl acetate / hexane to obtain 2 1 · 9 Kg-68 * This paper size applies to China National Hua (CNS) A4g grid (210 × 2Ήmm) ^ 1. ^ 1 In -1-! * = I- -1 «nn ml m · InTJ 03 (please read the notes on the back before filling this page) Μ B7 V. Description of the invention qc) Grams (88%) of α-(2-propylsulfonyl (Oxyimino) -3,4-dimethoxybenzyl gaseous, which is a ash-colored crystal and has a melting point of 90.5-93.5 ° C. The 1 H-NMR spectrum of the compound showed that it was a purified stereoisomer. The substance's UV spectrum (acetonitrile) shows a broad absorption band, with a maximum value of 346 micrometers (ε = 1 1 6 5 0 3 4), which extends to 434 micrometers. Elemental analysis: C i 3 H is 0 S S (312.34) C [%] Η [%] Ν [%] Calculated value: 49.99 5.16 8.97 Found value: 50.07 5.26 8.88 S Example S: ct — (2, 4, 6 -Reference (isopropyl) phenylsulfonyloxyimino) -3,4-dimethoxybenzyl fluoride as described in 1.2, 8.25 grams (0.44 mole) Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of α-Hydroxy Sub-Economy (please read the precautions on the back before filling this page) Amine 3,4-dimethoxybenzyl cyanide ib and 13.3 g (0.044 ) Of 2,4 * 6-ginsyl (isopropyl) benzenesulfonyl chloride in the presence of triethylamine to carry out the reaction. After the crude product was recrystallized from ethyl acetate / hexane, 14.25 g (75%) of "-(2,4,6-((isopropyl) phenylsulfonyloxyimino) -3", 4 Dimethoxy-benzyl cyanide M is obtained in the form of gray-brown crystals, which has a melting point of 90.5-9 3.5 TC. -69- This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) A7 printed by Shelley Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs ___B7__ 5. Description of the invention The 1 H-NMR spectrum of the compound shows that it is a purified product Stereoisomers. The substance's UV spectrum (acetonitrile) shows a broad absorption band, with a maximum at 3 52 μm (e = 1 1 0 0 0), which extends to 4 3 3 μm. Elemental analysis: C2 5 H3 2 N2 Os S (4 7 2. 6)

Cl%) Η [%] Ν [%} 計算值：6 3.5 4 6.8 2 5.9 3 發現值：63.44 6.72 5.8 1 實施例7: α — （η -辛基磺醢基氧亞胺基）一 3，4 — 二甲氣基苄基氰化物如1.2所述，10.3公克（Q.05莫耳）之α —羥基亞胺基一3，4 -二甲氧基苄基氰化物與11.7公克（0.055莫耳 )之 1_辛烷磺醯氛在三乙基胺的存在下進行反應。粗製產物自乙酸乙酯/己烷中進行再结晶後，19.1公克（37% )之α- (η—辛基磺醢基氧亞胺基）一 3，4一二甲氧基苄基氰化物以灰裼色结晶的形式得到，其具有熔點7 2 - 7 5C 。該化合物之1 Η— NMR光譜顯示其為一純化的立體異構物。該物霣的 UV光譜（乙購）顯示一廣泛的吸收帶，其最大值在3 4 9微毫米（e= 1 1 3 3 0)，其延伸至4 3 5微毫米。 -70- 本紙依尺度適用t國國家揉準（CNS) A4说格（210X297公釐） ---------ri------IT------^ (請先閲讀背面之注意事項再填寫本頁) Α? B7 經濟部中央橾準局具工消費合作社印褽五、發明説明（¢^) 兀素分析： C 1 8 Η 1 6 Ν 7 0 5 S (382.48) C [%} Η [%] N [X] 計蓴值： 56.53 6.85 7.32 發現值： 56.30 6.86 7.16 實施例8: C( - （4 —氢苯基磺醢基氧亞胺基）_3’4 一二甲氧基苄基氰化物如 1.2所述，10.3公克（0.05莫耳）之α —羥基亞胺基_3，4 一二甲氧基苄基氰化物與 12.2 公克（0.055 冥耳）之 4—氛苯磺酸氛化物在三乙基胺的存在下進行反應。粗製產物自乙酸乙酯/己烷進行再结晶後’ 15·9公克 (84%)之α— (4-氯苯基一磺醢基氧亞胺基）_3’4~ 二甲氧基苄基氰化物Κ淡黃色结晶的形式得到，其具有熔點 145.5-148.5t：。該化合物之1 H-fIMR光譜顯示其為 —纯化的立體異構物。該物質的UV光譜（乙膳）顯示一廣泛的吸收帶，其最大值在 350微奄米（ε= 1 1660)，其延伸至 4 3 7微毫米。元素分析：C ^ 6 Η ι 3 C 1 Νζ 〇5 S ( 380 . 80) c m η m ν m s u] ci m -7 Ι 本紙張尺度適用中國國家標準（CNS ) Α4洗格（210X297公釐） --------I — (請先鬩讀背面之注意事項再填寫本頁) ，νβ 線 A7 B7 五、發明説明ut) 計算值：5 0.4 7 3.4 4 7 . 3 6 8.4 2 9.3 1 發現值：5 0 . 50 3 . 4 6 7 . 3 7 8.4 2 9 . 3 3 實施例9: ot_ (甲基確睡基氧亞胺基）—4一甲基硫苄基氰化物類似於實施例3.4的製備方法，19.2公克（（].1莫耳 )之α -羥基亞胺基一 4 -甲基-硫苄基氰化物，於15.2 公克（0.15莫耳）之三乙基胺的存在下，與12.6公克（ 0.11莫耳）之甲烷磺醢氛進行反應。反應完成之後’得到 22.8 公克之灰裼色粗製產物，其自120奄升之乙酸乙酯中進行再结晶。14.0公克（52%)之α —(甲基磺醢基氧亞胺基）一4-甲基硫苄基氰化物Κ灰裼色结晶的形式得到 *其具有熔點 148-1505。該化合物之1 H-NMR光譜顯示其為一純化的立體異構物。該物質的UV光譜（乙腈）顯示一廣泛的吸收帶*其最大值在 349微«米（^ = 14 7 9 0 )，其延伸至4 4 0微毫米。 ---------&------1T------^ (請先Η讀背面之注意事項再填寫本頁) 經濟部中央樣隼局貝工消费合作社印製元素分析： C X 0 Η 1 0 Ν 2 〇 3 S 2 (270.30) C [X】 Η {%] Ν [5M s [%) 計算值： 44.43 3.73 10.36 23.72 發現值： 44.56 3.76 10.34 23.74 -72- 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） A7 B7 ____ 五、發明説明（) 實施例 10 : C(— （ 4一十二烷基苯基磺醢基氧亞胺基 )一 4一甲基硫苄基氰化物類似於實施例 3.4的製備方法，10.6公克（0.55莫耳）之〇(_羥基亞胺基一 4 —甲基一硫苄基氰化物*在 8.35公克（0.0825莫耳）之三乙基胺的存在下*與20.9 公克（0.06莫耳）之十二烷基苯磺醢氛進行反應。反應完成之後，得到黏稠狀棕色一灰褐色粗製產物，其經由色層分析於矽膠（洗提劑：石油醚/乙酸乙酯 20: 1)上進行純化。10.5 公克（38%)之α — （4 —十二烷基苯基磺醚基氧亞胺基）-4-甲基硫苄基氰化物以黃色一棕色黏掘狀液體的形式得到。該化合物之1 Η— NMR光譜顯示其為一纯 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央樣準局員工消費合作社印製化的立體異構物。該物質的 UV光譜（乙腈）顗示〜廣泛的吸收帶，其最大值在351微牽米（ε = 至 4 5 0微鼍米。 9750)，其延伸元素分析：C2 7 Hs e Νζ 〇3 S2 ( 5 0 0 . 72) cm Η [%] Ν [%] S [%] 計算值： 64 7 7 7.25 5.59 12.81 發現值： 64.72 7.29 5.58 12.76 -73- 本紙張尺度適用中國國家搮準（CNS ) Α4規格（2丨0Χ297公釐）經濟部中央標準局貝工消费合作社印製 A7 B7 五、發明説明實施例 11: 9一（4—甲基苯基磺醢基氧亞胺基）一 3 ，6—二甲氧基荛 11.1. 3，6_二甲氧基薄一 9 —詷 3，6—二甲氧基荛-9-萌經由 C. Chuang等人.in J. Am. Chem. Soc . 1 98 5 > 107， 4 2 38 所描述的多步驟合成加以製備。該據該方法，在最後一個合成步驟得到得到鈍化的 3，6—二甲氧基葬一 9_酮，其自該粗製產物的溶液中加以沉澱*其為淡黃色结晶而具有熔點139 — 144¾ ( 文獻值：142 - 144C)。該產物不經進一步的純化在下一個反應使用。經過滬縮之後，自母質疲體中沉澱析出一種淡黃色固體，其具有熔點 123 - 125"0。如文獻中所述，該固體除了 3 ，6—二甲氧基荛一9一酮K外，亦含有異構性化合物 1，6 -二甲氧基荛一9 -嗣。可從1 H-N MR光譜得知該混合物包括約 5 5%之3，6—二甲氧基荛一 9 一萌及45 %之1 ，6 —二甲氧基茺一9— _。此異構性混合物亦可不經進一步的纯化而用於後續反應步驟。 11.2. 9—羥基亞胺基—3，6 —二甲氧基荛 -74- 本紙張尺度逋用中國國家標準（CNS ) A4说格（2丨0X297公釐） ---------裝------訂------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局負工消费合作社印製 A7 B7__ 五、發明説明（^ /) 4.7公克（0.0195冥耳）之3，6_二甲氧基葬一9 一醣及2.7公克（0.039冥耳）之羥基一氯化銨於50笔升之乙酵及20毫升之水的混合物中進行加熱至9ϋυ。經過5 小時，將f溶疲倒入冰/水中並加入乙酸乙酯。將得到的懸浮疲進行過《並將已濾除的產物Μ水加Μ清洗並於真空狀態下進行乾爍。4.25公克（8 6%)之9 —羥基亞胺基一 3，6 —二甲氧基蒹Μ黃色固體形式得到，其具有熔點 230-240t：。根據1 H-NMR，粗製產物仍含有 3，6 -二甲氧基荛一 9 一調。該粗製產物，然而*不經進一步的鈍化而用於後讀步驟且不移除3，6 -二甲氧基蒹一 9 一酮直到纯化出終產物為止。元素分析：C i 5 Hi 3 N 0 3 (255.27) cm Η [%] N [%] 計算值： 70.58 5.13 5.49 發現值： 7 1.42 δ . 13 4.32 11.3 .9 - ( 4 —甲基苯基磺醢基氧亞胺基）一3，6- 二甲氧基 m 3.8 公克（〇. 015莫耳）之 9 一羥基亞胺基一3，6 — 二甲氧基椠及 2.3 公克（0 · 0 2 2 5 莫耳）之三乙基胺被懸 -75- 本紙張尺度適用中國國家揉率（CNS ) A4規格（210X297公釐） ---------------IT------^ (請先閲讀背面之注$項再填寫本頁) A7 B7 五、發明説明浮於 80笔升之四氫呋喃（THF)中且’在Ot ’逐滴加入 3.1公克（0.0165 莫耳）之對一甲苯磺酸氛化物於20奄升之 THF中所形成的溶液。經過4小時後，移除冰浴且將該反懕混合物於室溫下進行攪拌一整夜。随後加入 40« 升之 CH2 Cl2並將得到的銨鹽逋除。濾疲Μ水及飽和的 NaCl加以清洗，於硫酸鎂上進行乾燥且於一旋轉性揮發器中進行濃縮。得到的粗製產物經由快速色層分析在矽膠（洗提劑：石油醚/乙酸乙酯2:1)上進行純化。含有主產物的分疲被納於100 牽升之熱乙酵中並將該溶液在熱的時後過濾。在冷卻時，產物沉澱且被濾出並於真空狀態下進行乾煉。 3.2公克之（5 2%)之9— (4-甲基苯基磺醯基一氧亞胺基）一 3，6—二甲氧基薄K黃色结晶的肜式得到，其具有熔點143— 148=。該物霣的UV光譜（乙腈）顯示吸收帶最大值在 314微毫米（£=21100)，其延伸至4 50微毫米。元素分析：C2 2 Hi 9 NOs S ( 4 0 9 . 6) ---------,__裝-- (請先閲讀背面之注意事項再填寫本頁) 、ix 線經濟部中央樣準局貝工消費合作杜印製 [%] Η [%) Ν [%] 64.53 5.68 3.42 64.24 5.03 3.29 12 ： 9-( 4-十二 76 本紙張尺度適用中國國家標準（CNS ) A4現格（210X297公釐）經濟部中央標準局員工消费合作社印裝 A7 _B7_' 五、發明説明（y) )一 3，6—二甲氧基荛如11 . 3 .所述，5 . 1公克（0 . 0 2莫耳）之9 —羥基亞胺基一3，6 -二甲氧基興在〇υ，於3.0公克（0.03莫耳）之三乙基胺的存在下於100牽升之THF中，與5.6公克 ( 0 . 0 2 2 莫耳）之4一十二烷基苯磺醢氢進行反應。單雛後得到的粗製產物經由快速色層分析於矽膠（洗提劑：石油醚/乙酸乙酯4 : 1)上進行純化。5 . 8公克（5 1 . 3% ) 之9一（4—十二烷基—苯基磺醢基氧亞胺基）一 3，6—二甲氧基荛Μ黏稠狀黃色油狀物的形式得到。該物質的UV光’ 譜（乙腈）顯示吸收帶的最大值在315微奄米（e=21100 )，其延伸至4 4 3撤奄米。元素分析 C3 3 H4 i NOs S ( 5 6 3 . 7 6 ) C [%] η m N [%] sm 計算值： 70.31 7.33 2.48 5.69 發現值： 70.10 7.42 2.52 實施例13: 9_ (4-甲基苯基磺醢基氧亞胺基）一3 ，6 —二甲氧基第及9— (4_甲基苯基磺醢基氧亞胺基）一 1 ，6—二甲氧基莽的混合物 -77- 本紙張^度適用中國國家標準（〇犯）八4^格（210'乂297公釐） I--------丨^------ir------.^. (請先閱讀背面之注意事項再填寫本I) 經濟部中央標準局員工消費合作社印製 A7 B7___ 五、發明説明（2</>) 13.1. 9—羥基亞胺基-3，6—二甲氧基蒹及3-羥基亞胺基_1，6—二甲氧基豬將自實施例11.1的母質液體所單離得到的混合物’其包括約55% 3，6—二甲氧基蒹一 9一酮及 45%之1’6 — 二甲氧基荛一 9 -酮，以類似於實施例 11.2的製備方法，與羥基氛化铵在乙酵/水進行反應。得到灰裼色固髖*根據1 H-NMR，該固體包括約7 5%之9 —羥基亞胺基—3，6 一二甲氧基第及 2 5%之9 一羥基亞胺基一 1，6 -二甲氧基薄。粗製產物不經進一步的純化而用於後績的步驟。 13.2. 9— ( 4一甲基苯基磺醯基氧亞胺基）一 3，6- 二甲氧基薄及9 一（4 一甲基一苯基一磺醢基氧亞胺基）一 1 ，6_二甲氧基第來自實施例 13.1. (8.9公克，0.035莫耳）之粗製產物以類似於實施例11.3的製備方法於17 5毫升之THF在0 ·於5.3公克（0.0525莫耳）之三乙基胺的存在下，與 7.34公克（0. 0 38 5莫耳）之對一甲苯磺酸氛化物進行反懕而得到。得到的銨鹽被濾出且該溶液Μ飽和的氯化納溶疲加Μ清洗，於硫酸鎂上進行乾燥並於一旋轉性揮發器中進行濃縮。沉殺出來的粗製產物被溶解於熱乙酸乙酯中並進行過濾，且加入己烷。當該反應混合物靜置時，產物Κ黃 -7 8 _ 本紙张尺度適用中國國家標準（CNS ) Α4規格（210 X 297公釐） I I 裝訂線 (請先閲讀背面之注^^項再填寫本頁) 經濟部中央標準局員工消費合作社印製 Α7 Β7 五、發明説明色一灰褐色结晶的形式沉澱析出’該结晶為(4一甲基苯基磺醢基氧亞胺基）一3，6—二甲氧基荛及9一（4 一甲基一苯基磺醢基氧亞胺基）一 1，6-二甲氧基第的異構性混合物。產率為8 . 3公克（58% )，且熔點為141 一 148C ° 根據其1 H- NMR光譜，該混合物包括約之9— ( 4一甲基苯基磺醢基氧亞胺基）一 3，6—二甲氧基一蘋及3 Q % 9 -(4_甲基一苯基磺醢基氧亞胺基）一 1，6—二甲氧基一第。該混合物之UV光譜（乙腈）顯示吸收帶在314微毫米（ε =1867Q)，其延伸至440微毫米，具有長波長的最大值。元素分析：C2 2 Η! 9 NOs S ( 409.6) cm Η [%] Ν [%] S [%] 計算值： 64.53 4.68 3.42 7.83 發現值： 64.26 4.70 3 . 48 7.66 實施例 14: 9 一（4_十二烷基苯基磺醢基氧亞胺基 )_3，6-二甲氧基荛及9 一（ 4一十二烷基苯基磺醢基氧亞胺基）一 1*6 —二甲氧基荛之混合物如實施洌13.2.所述，來自實施例13.1.之8.9公克（ 0.035 莫耳）之粗製產物於THF中，在三乙基胺的存在下 ’與 13.2公克（0.038奠耳）之4 -十二烷基-苯磺醢 -79- 本紙張尺度適用中國國家揉準（CNS ) Α4規格（2丨Ο X 297公釐） ---------------IT------.^ (請先聞讀背面之注意事項再填寫本頁) 經濟部中央樣準局員工消費合作社印裝 A7 B7_ 五、發明説明（7幻氮進行反應。得到的油狀物之為粗製產物，其經由兩次快速色層分析於矽膠（洗提劑：石油醚/乙酸乙酯9:1，隨後石油醚/乙酸乙酯 3: 1)上進行純化。13.0公克（66 %)之9- ( 4一十二烷基苯基磺醢基氧亞胺基）一 3 * 6- 二甲氧基荛及9_ (4-十二烷基苯基磺醢基氧亞胺基）一 1，6-二甲氧基莽以黏稠狀淺紅色油狀物的形式得到。根據其1 H-NMR光譜，該混合物包括約7 5%之9- (4 一十二烷基苯基磺醢基氧亞胺基）_3，6—二甲氧基蒹及 25%之 9 一（4 一十二烷基苯基磺醢基氧亞胺基）_1，6_二甲氧基莞。該混合物之UV光譜（乙腈）顯示吸收帶，其在315 微毫米（ε = 1 8 3 30)，其延伸至4 4 5微毫米，具有長波長的最大值。元素分析：C3 3 IU 1 HOs S ( 5 6 3 . 7 6 ) C [%] Η [%] Ν [%] sm 計算值： 70.31 7.33 2.48 5.69 發現值： 70.31 7.37 2.47 5.37 實施例 15: c(- （3-三氟甲基苯基磺醢基氧亞胺基 )一3，4 一二甲氧基苄基氰化物如1.2.所述， 4.1公克（0.02莫耳）之α —羥基亞 _ 8 0 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） --------------IT------^ (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消费合作杜印製 A7 _B7_ 五、發明説明胺基一 3，4一二甲氧基苄基氰化物與5·4公克（0.022其耳）之 3-三氟甲基苯基磺酸氯化物在三乙基胺的存在下進行反應。經粗製產物自乙酸乙酯/ 一己垸的進行再结晶後， 6.6公克（80%) of α — (3 -三氟甲基一苯基磺醢基氧亞胺基）一3，4 —二甲氧基苄基氰化物K淡黃色结晶的形式得到，其具有熔點 129-130=。該化合物之1 Η - N MR光譜顯示其為純化的立體異構物。該物質的UV光譜 (乙膈）顯示一廣泛的吸收帶，其於351微笔米（E = 11700)，其延伸至 430微毫米，具有最大值。元素分析 C ! 7 Η 丄 3 F3 N2 0 5 S (414.36) C [X] Η [X] N [%] S [%] 計算值：49.283.16 6.76 7.74 發現值：4 9 . 4 7 3 . 3 3 6.8 5 7.7 9 賣施例16:α - （苯基磺醢基氧亞胺基）一 3，4一二甲氧基苄基氰化物如1.2.所述，10.3公克（0.05莫耳）之cx —羥基亞胺基一3，4 —二甲氧基苄基氰化物與 9.71 公克（0.055 莫耳）之4 -苯磺酸氛化物在7.6公克之三乙基胺的存在下進行反應。在粗製產物自乙酸乙酯/己烷中進行再结晶之本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) •裝. 訂經濟部中央標準局貝工消费合作社印製 A7 __B7_ 五、發明説明（#1 後，11· 1公克（64%)之α -(苯基一磺醢基氧亞胺基 )一 3，4 一二甲氧基苄基氰化物Κ淡黃色结晶的形式得到，其具有熔點 138.5- 1421C。該化合物之1 H-NMR光譜顯示其為一純化的立鼉異構物。該物質之UV光譜（乙腈）顯示一廣泛的吸收帶，其最大值在 350微蠹米（ε= 1 1370)，其延伸至436微毫米。元素分析：Ci 6 Hi 4 05 S ( 3 4 6 . 3 6) C [X] Η [%] Ν [%] S [%] 計算值： 55.48 4.07 θ.03 9.29 發現值： 55.51 4.1 2 8 . 1 0 9.28 經由將母質液體進行揮發，得到2.6公克之灰褐色物質，其熔點104-110C，藉由1 H-NMR-分析證實其為α 一（苯基一磺醢基氧亞胺基）一3，4一二甲氧基苄基氛化物之（Ζ)—及（Ε)—異構物的混合物（比例ca. 2 : 1) 〇實施例 17: α_ (4—甲氧基苯基磺醢基氧亞胺基）一 3，4一二甲氧基苄基氛化物如 1.2·所述，10.3公克（0.Q5莫耳）之α —羥基本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） --------------IT------.^ (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消费合作杜印装 A7 _ B7_ 五、發明説明（;^) 亞胺基一3，4一二甲氧基苄基氰化物與 11.37 公克（ 0.0 5 5 莫耳）之4一甲氧基苯基磺酸氮化物在？· 6公克之三乙基胺的存在下進行反應。經粗製產物於乙酸乙酯/己烷中進行再结晶後，3·26公克（17%)之α— (4 -甲氧基—苯基磺醢基氧亞胺基）一 3，4_二甲氧基苄基氰化物 Κ淡黃色结晶形式得到，其具有熔點1 6 1 - 1 6 7 Ό。該化合物之1 Η — NMR光譜顯示其為一純化的立體異構物。該物質之UV光譜（乙腈）顯示一廣泛的吸收帶，其最大值在349 微奄米（ε = 117QQ)，其延伸至435微毫米。元素分析：C i 7 H i s Ν2 〇6 S ( 3 7 6 . 38) CU] Η [%} N [X] S [%] 計算值： 54.25 4 28 7.44 8.52 發現值： 54.16 4.2 3 7 . 3 5 8 . 4 7 實施洌 18:α_ (4-硝基苯基磺醢基氧亞胺基）一 3，4一二甲氧基苄基氰化物根據1.2 所敘述的方法，α —羥基亞胺基一3，4 一二 -甲氧基苄基氰化物及 4一硝基苯基磺酸氛化物進行反應。物理數據為示於表A。本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） --------- I I n ϋ n T I I I I---- (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 A7 _B7_ 五、發明説明（P) 實施例 19: 9 一（π-辛基確藤基氧亞胺基）一 3，6 一二甲氧基荛如11 . 3.所述，2. 55公克（〇. 〇1莫耳）之9-羥基亞胺基一 3，6—二甲氧基第在 ’於1.5公克（0.015 莫耳）之三乙基胺的存在下在60 毫升之 THF中，與2·34 公克（0.011冥耳）之π—辛基確醢氛進行反應。在簞離後得到的粗製產物經由自乙酸乙醋中進行再结晶進行纯化。得到2 . 2 公克（5 1 % )之黃色一灰裼色结晶形式之9 一 (η _辛基_磺釀基氧亞胺基）一 3，6—二甲氧基蒡，其具有熔點 105 — 110七。該物質之UV光譜（乙腈）顯示一廣泛的吸收帶，其最大值在 313微毫米（ε = 2 0 6 2 0 ) ’其延伸至 4 4 5微毫米。元素分析：CZ 3 ΗΖ 9 N0S S ( 431 . 55) C [%) H[%] NU] S[%] 計算值：64. 0 1 6 . 7 7 3 . 2 5 7 . 4 3 發現值：63.906.80 3.40 7.28 實施例20: α— (2 —丙基磺皤基氧亞胺基）―4 一甲基硫苄基氰化物 -84" 本紙張尺度適用中國國家榡準（CNS > A4規格（210X 297公釐） I --------K裝------訂------線 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 A7 __B7 _ 五、發明説明（iI ) 類似於實施例3.4的製備方法，9.6公克（0.5莫耳 )之ct 一羥基亞胺基一 4 一甲基-硫苄基氰化物，在7.6公克（0.075 莫耳）之三乙基胺的存在下，與7.85 公克（ 0.055 莫耳）之2—丙烷磺醢氯進行反應。反應完成後，粗製產物自乙酸乙酷/己烷中進行再结晶。 11.1公克（ 83%)之α — （2-丙基磺醢基氧一亞胺基）一 4-甲基硫苄基氰化物以灰裼色结晶的形式得到，其具有熔點83-87 力。該化合物之1 Η- NMR光譜顯示其為純化的立體異構物。該物霣之UV光譜（乙腈）顯示一廣泛的吸收帶，其最大值在 35Q微毫米（e二1 4 6 6(3 )，其延伸至 4 3 5微毫米。元素分析：Ct 2 Hi 4 H2 〇3 S2 ( 266.32) cm Η [%] Ν [%} s m 1 計算值： 48.30 4.72 9.38 21.49 發現值： 48.19 4.79 9.50 2 1.85 實施例21: α — （4 —甲基苯基磺醢基氧亞胺基）-3 ，4 一雙（甲基硫）苄基氰化物 21·1. 1，2—雙（甲基硫）苄 1，2 —雙（甲基硫）苯自硫酚根據 M. Dotze等人， ~ 8 5 本紙張尺度適用中國國家橾準（CNS ) Α4規格（210X297公釐） ---------ir^------IT------^ (請先Μ讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印裝 A7 B7_ 五、發明説明（斤幻Cl%) Η [%] Ν [%} Calculated value: 6 3.5 4 6.8 2 5.9 3 Found value: 63.44 6.72 5.8 1 Example 7: α — (η -octylsulfonyloxyimino) -3, 4-Dimethylaminobenzyl cyanide as described in 1.2, 10.3 g (Q.05 mole) of α-hydroxyimino-3,4-dimethoxybenzyl cyanide and 11.7 g (0.055 mole) Ear) 1-octanesulfonium is reacted in the presence of triethylamine. After the crude product was recrystallized from ethyl acetate / hexane, 19.1 g (37%) of α- (η-octylsulfonyloxyimino) -3,4-dimethoxybenzyl cyanide Obtained in the form of grayish-colored crystals, which have a melting point of 7 2-7 5C. The 1 Η-NMR spectrum of the compound showed that it was a purified stereoisomer. The UV spectrum of the material (Eco) shows a broad absorption band with a maximum value of 3 4 9 μm (e = 1 1 3 3 0), which extends to 4 3 5 μm. -70- This paper is suitable for national standards (CNS) A4 (210X297 mm) according to the standard --------- ri ------ IT ------ ^ (please first Read the notes on the reverse side and fill out this page) Α? B7 Seal of the Central Consumers' Association of Japan Ministry of Economic Affairs and Industrial Cooperatives Co., Ltd. 5. Description of Invention (¢ ^) Element analysis: C 1 8 Η 1 6 Ν 7 0 5 S (382.48 ) C [%} Η [%] N [X] calculated value: 56.53 6.85 7.32 found value: 56.30 6.86 7.16 Example 8: C (-(4-hydrophenylsulfonyloxyimino) _3'4 Monodimethoxybenzyl cyanide as described in 1.2, 10.3 grams (0.05 moles) of α-hydroxyimino_3,4 dimethoxybenzyl cyanide and 12.2 grams (0.055 moles) 4-Aminobenzenesulfonic acid is reacted in the presence of triethylamine. After recrystallization of the crude product from ethyl acetate / hexane, '15 · 9 g (84%) of α- (4-chlorophenyl) Monosulfonyloxyimino) _3'4 ~ Dimethoxybenzyl cyanide K is obtained in the form of pale yellow crystals, which has a melting point of 145.5-148.5t. The 1 H-fIMR spectrum of this compound shows that it is- Purified stereoisomers. UV spectrum of the substance ( It shows a broad absorption band with a maximum of 350 μm (ε = 1 1660), which extends to 4 3 7 μm. Elemental analysis: C ^ 6 ι 3 C 1 Νζ 〇5 S (380 80) cm η m ν msu] ci m -7 Ι This paper size applies to the Chinese National Standard (CNS) Α4 wash case (210X297 mm) -------- I — (Please read the note on the back first Please fill in this page again), νβ line A7 B7 V. Invention description ut) Calculated value: 5 0.4 7 3.4 4 7. 3 6 8.4 2 9.3 1 Found value: 5 0. 50 3. 4 6 7. 3 7 8.4 2 9.3 3 Example 9: ot_ (methyl surelyloxyimino) -4-methylthiobenzyl cyanide is similar to the preparation method of Example 3.4, 19.2 g (() .1 mole) of α-Hydroxyimino- 4-methyl-thiobenzyl cyanide, reacted with 12.6 g (0.11 mol) of methanesulfonium in the presence of 15.2 g (0.15 mol) of triethylamine After the reaction was completed, '22 .8 grams of a crude ochre-colored product was obtained which was recrystallized from 120 liters of ethyl acetate. 14.0 grams (52%) of α- (methylsulfonyloxyimino)- 4-methylthiobenzyl The cyanocyanide K is obtained in the form of grayish-colored crystals * which has a melting point of 148-1505. The 1 H-NMR spectrum of the compound showed that it was a purified stereoisomer. The substance's UV spectrum (acetonitrile) shows a broad absorption band * with a maximum at 349 micrometers (^ = 14 7 9 0), which extends to 4 40 micrometers. --------- & ------ 1T ------ ^ (Please read the notes on the back before filling this page) Analysis of system elements: CX 0 Η 1 0 Ν 2 〇3 S 2 (270.30) C [X] Η {%] Ν [5M s [%) Calculated value: 44.43 3.73 10.36 23.72 Found value: 44.56 3.76 10.34 23.74 -72- This paper size applies to Chinese National Standard (CNS) A4 specification (210 × 297 mm) A7 B7 ____ V. Description of the invention () Example 10: C (-(4-dodecylphenylsulfonyloxyimino) A 4-monomethylthiobenzyl cyanide is similar to the preparation method of Example 3.4, 10.6 grams (0.55 moles) of 0 (-hydroxyimino-4 -methyl monothiobenzyl cyanide * at 8.35 grams ( 0.0825 mole) in the presence of triethylamine * and reacted with 20.9 g (0.06 mole) of dodecylbenzenesulfonic acid atmosphere. After the reaction was completed, a viscous brown-grey brown crude product was obtained. Layer analysis was purified on silica gel (eluent: petroleum ether / ethyl acetate 20: 1). 10.5 g (38%) of α- (4-dodecylphenylsulfonyl) Imine) -4-methylthiobenzyl cyanide was obtained as a yellow-brown sticky liquid. 1 化合物 -NMR spectrum of the compound shows that it is pure (please read the precautions on the back before filling in this Page) Stereoisomers printed by the Consumer Cooperative of the Central Bureau of Prospecting, Ministry of Economic Affairs. The UV spectrum (acetonitrile) of this substance is shown to show a wide range of absorption bands, the maximum of which is 351 micrometers (ε = to 4 5 0 μ 鼍 m. 9750), its extended elemental analysis: C2 7 Hs e Νζ 〇3 S2 (50 0 .72) cm Η [%] Ν [%] S [%] Calculated value: 64 7 7 7.25 5.59 12.81 Found value: 64.72 7.29 5.58 12.76 -73- This paper size is applicable to China National Standard (CNS) A4 specification (2 丨 0 × 297 mm) Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention Example 11 : 9- (4-methylphenylsulfonyloxyimino) -3,6-dimethoxyfluorene 11.1.1,3,6-dimethoxypropane-9-fluorene 3,6-dimethoxy Mole-9-Meng was prepared via a multi-step synthesis as described by C. Chuang et al. In J. Am. Chem. Soc. 1 98 5 > 107, 4 2 38According to this method, a passivated 3,6-dimethoxypyridine-9-one is obtained in the last synthesis step, which is precipitated from the solution of the crude product * which is a pale yellow crystal with a melting point of 139-144¾ (Literature value: 142-144C). This product was used in the next reaction without further purification. After shrinking in Shanghai, a light yellow solid precipitated from the matrix fatigue, which had a melting point of 123-125 " 0. As described in the literature, this solid contains, in addition to 3,6-dimethoxyfluoren-9-one ketone K, an isomeric compound 1,6-dimethoxyfluoren-9-fluorene. It can be known from the 1 H-N MR spectrum that the mixture includes about 5 5% of 3,6-dimethoxyfluorene-9-methyl and 45% of 1,6-dimethoxyfluorene-9-methyl. This isomeric mixture can also be used in subsequent reaction steps without further purification. 11.2. 9-Hydroxyimino-3,6-dimethoxy 甲 -74- This paper uses Chinese National Standard (CNS) A4 standard (2 丨 0X297 mm) -------- -Installation ------ Order ------ line (please read the notes on the back before filling this page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives A7 B7__ 5. Description of the invention (^ /) 4.7 g (0.0195 hare ear) of 3,6_dimethoxy funnel-9 monosaccharide and 2.7 g (0.039 hale ear) of hydroxymonoammonium chloride in a mixture of 50 liters of acetic acid and 20 ml of water Heat to 9ϋυ. After 5 hours, the solvent was poured into ice / water and ethyl acetate was added. The obtained suspension was washed, and the filtered product M was washed with water plus M and dried under vacuum. 4.25 g (8 6%) of 9-Hydroxyimino- 3,6-dimethoxy 蒹 M is obtained as a yellow solid, which has a melting point of 230-240t :. According to 1 H-NMR, the crude product still contained 3,6-dimethoxyfluorene-9. This crude product, however, was used in the read-back step without further passivation and 3,6-dimethoxyfluoren-9-one was not removed until the final product was purified. Elemental analysis: C i 5 Hi 3 N 0 3 (255.27) cm Η [%] N [%] Calculated: 70.58 5.13 5.49 Found: 7 1.42 δ. 13 4.32 11.3 .9-(4-methylphenylsulfonate Fluorenyloxyimino)-3,6-dimethoxym 3.8 g (0.015 mol) of 9 monohydroxyimino-3,6-dimethoxyfluorene and 2.3 g (0 · 0 2 2 5 mol) of triethylamine suspended -75- This paper size applies to China National Kneading Rate (CNS) A4 (210X297 mm) --------------- IT ------ ^ (Please read the note on the back before filling this page) A7 B7 V. Description of the invention Floating in 80 liters of tetrahydrofuran (THF) and adding 3.1 g (0.0165) dropwise in Ot Mol) solution of p-toluenesulfonic acid in 20 liters of THF. After 4 hours, the ice bath was removed and the reaction mixture was stirred at room temperature overnight. Then 40 liters of CH2Cl2 was added and the resulting ammonium salt was decanted. The water and saturated NaCl were filtered, washed, dried over magnesium sulfate and concentrated in a rotary volatilizer. The resulting crude product was purified by flash chromatography on silica gel (eluent: petroleum ether / ethyl acetate 2: 1). The fractions containing the main product were taken up in 100 liters of hot ethyl acetate and the solution was filtered after the hot time. Upon cooling, the product precipitated and was filtered off and dried under vacuum. 3.2 g (52%) of 9- (4-methylphenylsulfonyloxyimino)-3,6-dimethoxy thin K-yellow crystals is obtained by the formula, which has a melting point of 143- 148 =. The UV spectrum (acetonitrile) of this compound showed a maximum absorption band of 314 μm (£ = 21100), which extended to 4 50 μm. Elemental analysis: C2 2 Hi 9 NOs S (4 0 9. 6) ---------, __ equipment-(Please read the precautions on the back before filling this page), ix center of the Ministry of Economy Printed by the Bureau of Specimen Bureau Consumer Cooperation [%] Η [%] Ν [%] 64.53 5.68 3.42 64.24 5.03 3.29 12 ： 9- (4-12 76 This paper is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) A7 _B7_ 'printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention (y)) 3,6-dimethoxyfluorene as described in 11.3, 5.1g (0 0 2 mole) of 9-hydroxyimino-3,6-dimethoxy group in 0υ, in the presence of 3.0 g (0.03 mole) of triethylamine in 100 draft THF , And react with 5.6 g (0.022 mol) of 4-dodecylbenzenesulfonium hydrogen. The crude product obtained after a single chick was purified on a silica gel (eluent: petroleum ether / ethyl acetate 4: 1) by rapid color layer analysis. 5.8 g (5 1.3%) of 9- (4-dodecyl-phenylsulfonyloxyimino) -3,6-dimethoxy 荛 M viscous yellow oil Get the form. The UV light spectrum (acetonitrile) of this material shows that the maximum absorption band is 315 μm 2 (e = 21100), which extends to 4 4 3 m 2. Elemental analysis C3 3 H4 i NOs S (5 6 3. 7 6) C [%] η m N [%] sm Calculated value: 70.31 7.33 2.48 5.69 Found value: 70.10 7.42 2.52 Example 13: 9_ (4-methyl A mixture of phenylsulfonyloxyimino), 3,6-dimethoxy and 9- (4-methylphenylsulfonyloxyimino), 1,6-dimethoxyl -77- This paper is ^ degree applicable to the Chinese national standard (zero offenses) 8 4 ^ grid (210 '乂 297 mm) I -------- 丨 ^ ------ ir ----- -. ^. (Please read the notes on the back before filling in this I) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7___ V. Description of the invention (2 < / >) 13.1. 9-Hydroxyimino-3 , 6-Dimethoxyfluorene and 3-hydroxyimino-1,6-dimethoxypig The mixture obtained by separating from the mother liquid of Example 11.1 ', which includes about 55% 3,6- Dimethoxyfluorene-9-one and 45% of 1'6-dimethoxyfluorene-9-one were reacted in a similar manner to that in Example 11.2 with hydroxyaminated ammonium in acetic acid / water. Obtained a gray-colored solid hip * According to 1 H-NMR, the solid includes about 7 5% of 9-hydroxyimino-3,6-dimethoxythion and 2 5% of 9-hydroxyimino-1 , 6-dimethoxy thin. The crude product was used in subsequent steps without further purification. 13.2. 9- (4-methylphenylsulfonyloxyimino)-3,6-dimethoxy thin and 9- (4-methylphenylphenylsulfonyloxyimino)- The 1,6-dimethoxydiamine was obtained from the crude product of Example 13.1. (8.9 g, 0.035 mol) in a manner similar to that of Example 11.3 in 17 5 ml of THF at 0 · 5.3 g (0.0525 mol). ), In the presence of triethylamine, and 7.34 g (0.038 5 mol) of p-toluenesulfonic acid ammonium compound is obtained by inversion. The obtained ammonium salt was filtered off and the solution was saturated with sodium chloride, washed with sodium chloride, dried over magnesium sulfate, and concentrated in a rotary volatilizer. The settled crude product was dissolved in hot ethyl acetate and filtered, and hexane was added. When the reaction mixture is left to stand, the product K yellow-7 8 _ This paper size applies to the Chinese National Standard (CNS) A4 size (210 X 297 mm) II gutter (please read the note ^^ on the back before filling in this Page) Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the invention-A gray-brown crystal precipitates in the form of '4-methylphenylsulfonyloxyimino group]-3, 6 -An isomeric mixture of dimethoxyfluorene and 9- (4-methyl-phenylsulfonyloxyimino) -1,6-dimethoxydi. The yield was 8.3 g (58%), and the melting point was 141 to 148 ° C. According to its 1 H-NMR spectrum, the mixture included about 9- (4-methylphenylsulfonyloxyimino)- 3,6-dimethoxy-methyl and 3 Q% 9- (4-methyl-phenylsulfonyloxyimino) -1,6-dimethoxy-first. The UV spectrum (acetonitrile) of the mixture shows an absorption band at 314 micrometers (ε = 1867Q), which extends to 440 micrometers and has a long wavelength maximum. Elemental analysis: C2 2 Η! 9 NOs S (409.6) cm Η [%] Ν [%] S [%] Calculated value: 64.53 4.68 3.42 7.83 Found value: 64.26 4.70 3. 48 7.66 Example 14: 9 one (4 _Dodecylphenylsulfonyloxyimino) _3,6-dimethoxyfluorene and 9- (4-dodecylphenylsulfonyloxyimino) -1 * 6-di The mixture of methoxyfluorene was as described in Implementation 13.2. The crude product from Example 13.1. Of 8.9 g (0.035 mol) was dissolved in THF in the presence of triethylamine and 13.2 g (0.038 mol). ) Of 4 -Dodecyl-benzenesulfonium-79- This paper size is applicable to China National Standard (CNS) Α4 size (2 丨〇 X 297 mm) ------------- --IT ------. ^ (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs A7 B7_ 5. Description of the invention (7 Magic nitrogen reaction. Get The crude oil was a crude product, which was purified on silica gel (eluent: petroleum ether / ethyl acetate 9: 1, followed by petroleum ether / ethyl acetate 3: 1) via two flash chromatography. 13.0 9 grams (66%) Phenylphenylsulfonyloxyimino)-3 * 6-dimethoxyfluorene and 9_ (4-dodecylphenylsulfonyloxyimino)-1,6-dimethoxymethyl Obtained as a viscous pale red oil. According to its 1 H-NMR spectrum, the mixture includes about 7 5% of 9- (4-dodecylphenylsulfonyloxyimino) -3,6. —Dimethoxyfluorene and 25% 9- (4-dodecylphenylsulfonyloxyimino) _1,6-dimethoxycarbonate. The UV spectrum (acetonitrile) of the mixture shows the absorption band , Which is at 315 μm (ε = 1 8 3 30), which extends to 4 4 5 μm and has a long wavelength maximum. Elemental analysis: C3 3 IU 1 HOs S (5 6 3. 7 6) C [ %] Η [%] Ν [%] sm Calculated value: 70.31 7.33 2.48 5.69 Found value: 70.31 7.37 2.47 5.37 Example 15: c (-(3-trifluoromethylphenylsulfonyloxyimino)- 3,4 Dimethoxybenzyl cyanide as described in 1.2. 4.1 g (0.02 mol) of α-Hydroxy_ 8 0 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -------------- IT ------ ^ (Please read the note on the back first Please fill in this page for further information) Consumption cooperation between employees of the Central Bureau of Standards, Ministry of Economic Affairs, Du printed A7 _B7_ V. Description of the invention Amino-3,4-dimethoxybenzyl cyanide and 5.4g -The trifluoromethylphenylsulfonic acid chloride is reacted in the presence of triethylamine. After recrystallizing the crude product from ethyl acetate / hexane, 6.6 g (80%) of α- (3-trifluoromethyl-phenylsulfonyloxyimino) -3,4-dimethyl Oxybenzyl cyanide K is obtained in the form of pale yellow crystals, which has a melting point of 129-130 =. The 1 Η -N MR spectrum of the compound showed that it was a purified stereoisomer. The substance's UV spectrum (acetylene) shows a broad absorption band at 351 micrometers (E = 11700), which extends to 430 micrometers with a maximum. Elemental analysis C! 7 Η 丄 3 F3 N2 0 5 S (414.36) C [X] Η [X] N [%] S [%] Calculated: 49.283.16 6.76 7.74 Found: 4 9. 4 7 3. 3 3 6.8 5 7.7 9 Selling Example 16: α- (phenylsulfonyloxyimino) -3,4-dimethoxybenzyl cyanide as described in 1.2. 10.3 g (0.05 mole) The reaction of cx-hydroxyimino-3,4-dimethoxybenzyl cyanide with 9.71 g (0.055 mol) of 4-benzenesulfonic acid odorant was carried out in the presence of 7.6 g of triethylamine. The paper size of the crude product recrystallized from ethyl acetate / hexane is applicable to the Chinese National Standard (CNS) A4 size (210X297 mm) (please read the precautions on the back before filling out this page). Printed by the Central Bureau of Standards, Shellfish Consumer Cooperative A7 __B7_ V. Description of the invention (after # 1, 11.1 g (64%) of α- (phenyl-sulfonyloxyimino group)-3, 4-12 The methoxybenzyl cyanide K is obtained in the form of pale yellow crystals, which has a melting point of 138.5-1421C. The 1 H-NMR spectrum of the compound shows that it is a purified sterilomer isomer. UV spectrum (acetonitrile) of the substance Shows a broad absorption band with a maximum value of 350 μm (ε = 1 1370), which extends to 436 μm. Elemental analysis: Ci 6 Hi 4 05 S (3 4 6. 3 6) C [X] Η [%] Ν [%] S [%] Calculated value: 55.48 4.07 θ.03 9.29 Found value: 55.51 4.1 2 8. 1 0 9.28 By volatilizing the mother liquid, 2.6 g of gray-brown material was obtained, and its melting point 104-110C, which was confirmed to be α- (phenyl-sulfonyloxyimino) -3,4-dimethoxybenzyl by 1 H-NMR-analysis A mixture of (Z) — and (E) —isomers (ratio ca. 2: 1) 〇 Example 17: α_ (4-methoxyphenylsulfonyloxyimino)-3, 4-Dimethoxybenzyl odorant, as described in 1.2 ·, 10.3 grams (0.Q5 mole) of α-hydroxyl This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)- ------------ IT ------. ^ (Please read the precautions on the back before filling out this page) The Central Bureau of Standards of the Ministry of Economic Affairs Shellfish Consumer Cooperation Du printed A7 _ B7_ 5 、 Explanation of the invention (; ^) imine-3,4-dimethoxybenzyl cyanide and 11.37 g (0.0 5 5 mol) of 4-methoxyphenylsulfonic acid nitride in? 6 g The reaction was carried out in the presence of triethylamine. After recrystallization of the crude product in ethyl acetate / hexane, 3.26 g (17%) of α- (4-methoxy-phenylsulfonyl) Oxyimino)-3,4-dimethoxybenzyl cyanide K is obtained in the form of pale yellow crystals, which has a melting point of 1 6 1-1 6 7 Ό. 1 该 of this compound — NMR spectrum shows that it is a purified Stereoisomers. UV light of the substance (Acetonitrile) shows a broad absorption band with a maximum value of 349 μ 奄 m (ε = 117QQ), which extends to 435 μm. Elemental analysis: C i 7 H is Ν 2 〇 6 S (3 7 6. 38) CU] Η [%} N [X] S [%] Calculated: 54.25 4 28 7.44 8.52 Found: 54.16 4.2 3 7. 3 5 8. 4 7 Implementation of 洌 18: α_ (4-nitrophenylsulfonium Oxyimino)-3,4-dimethoxybenzyl cyanide According to the method described in 1.2, α-hydroxyimino- 3,4-di-methoxybenzyl cyanide and 4-mononitrate The phenyl sulfonic acid is reacted. The physical data are shown in Table A. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) --------- II n ϋ n TIII I ---- (Please read the precautions on the back before filling this page) Economy Printed by the Central Bureau of Standards, Shellfish Consumer Cooperatives A7 _B7_ V. Description of the Invention (P) Example 19: 9-(π-octyl-Cetyloxyimine)-3, 6-Dimethoxyfluorene such as 11 3. As mentioned, 2.55 g (0.01 mol) of 9-hydroxyimino- 3,6-dimethoxy di-diethylamine at 1.5 g (0.015 mol) In the presence of THF in 60 ml of THF, it was reacted with 2.34 g (0.011 hare) of π-octyl sure atmosphere. The crude product obtained after decantation was purified by recrystallization from ethyl acetate. 2.2 g (51%) of yellow-grey ochre crystal form of 9-((n-octyl_sulfonyloxyimino) -3,6-dimethoxyfluorene having a melting point of 105 — 110 seven. The substance's UV spectrum (acetonitrile) shows a broad absorption band, with a maximum value of 313 μm (ε = 2 0 6 2 0) ′ which extends to 4 4 5 μm. Elemental analysis: CZ 3 ΗZ 9 N0S S (431. 55) C [%) H [%] NU] S [%] Calculated value: 64. 0 1 6. 7 7 3. 2 5 7. 4 3 Found value: 63.906.80 3.40 7.28 Example 20: α- (2-propylsulfonyloxyimino) -4 monomethylthiobenzyl cyanide-84 " This paper size applies to China National Standards (CNS > A4 Specifications (210X 297mm) I -------- K Pack -------- Order ------ Line (Please read the precautions on the back before filling out this page) Central Bureau of Standards, Ministry of Economic Affairs Printed by employee consumer cooperative A7 __B7 _ 5. Description of the invention (iI) Similar to the preparation method of Example 3.4, 9.6 g (0.5 mol) of ct-hydroxyimino-4-methyl-thiobenzyl cyanide, In the presence of 7.6 g (0.075 mol) of triethylamine, the reaction was carried out with 7.85 g (0.055 mol) of 2-propanesulfonyl chloride. After the reaction was completed, the crude product was subjected to ethyl acetate / hexane. Recrystallized 11.1 g (83%) of α- (2-propylsulfonyloxy-imino) -4-methylthiobenzyl cyanide is obtained in the form of grayish-colored crystals, which has a melting point of 83- 87 forces. 1 of the compound -NMR spectrum shows that it is a purified stereoisomer. The UV spectrum (acetonitrile) of this substance (显示) shows a wide absorption band, with a maximum value of 35Q micromm (e 2 1 4 6 6 (3), which extends to 4 3 5 μm. Elemental analysis: Ct 2 Hi 4 H2 〇3 S2 (266.32) cm Η [%] Ν [%} sm 1 Calculated value: 48.30 4.72 9.38 21.49 Found value: 48.19 4.79 9.50 2 1.85 Example 21: α — (4-methylphenylsulfonyloxyimino) -3,4 bis (methylsulfanyl) benzyl cyanide 21.1.1,2-bis (methylsulfanyl) benzyl1,2 —Bis (methylthio) benzene from thiophenol According to M. Dotze et al., ~ 8 5 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) --------- ir ^ ------ IT ------ ^ (Please read the precautions on the back before filling out this page) Printed by A7 B7, Shellfish Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs

Phosphorus * Sulfur » and Silicon 1993» 84， 95中所述的步驟進行製備。其為一淡黃色油狀物’具有沸點154 C/22牽巴，並Μ產率29%得到。 21.2. 1，2 —雙（甲基硫）一 4一氛甲基一苯 46公克（0· 3 4 3莫耳）之 A1C13被懸浮於2 00毫升之 1，2—二氯乙烷中且，在 0C，加入9.1公克（0.12 莫耳）之甲醒二甲基乙醛。随後逐滴加入17_〇公克（0.1 莫耳）之1，2_雙-（甲基硫）苯且該懸浮疲被加熱至室溫。當起始物質不再能由 GC分析偵测到時，將該溶疲倒入冰/水中且將該有機相分離並於硫酸鎂上進行乾燥。當該溶劑已被蒸發去除時，12.1公克（55%)之1，2 -雙 (甲基硫）一4一氛甲基一苯Κ黃色油狀物的形式得到。該化合物之1H-NMR 光譜（CDC13)與被建議的结構吻合： 7. 17-7.13， s 及 d， 3 芳香性 Η; 452， s， 2H ；2.44， s， CH3 S 及 2·43， s， CH3 S。 21.3. 3，4一雙（甲基硫）苄基氰化物 42.5公克（0.194冥耳）之1，2 -雙（甲基硫）-4 一氢甲基一苯及 25.3公克（0.388莫耳）之氰化鉀在周圍溫度下於20(1毫升之DMS0中進行攪拌。當起始物質不再 -8 6 _ 本紙張尺度適用中國國家梂準（CNS ) A4规格（210X297公釐） ---------裝------訂------線 (請先閲讀背面之注意事項再填寫本I) 經濟部中央標準局貝工消費合作杜印裝 A7 _B7_ 五、發明说明（fj) 被 GC分析偵測到時，將棕色溶液傾倒入冰/水中並Μ乙酸乙酷進行萃取且該有機相於硫酸鎂上進行乾燥。經遇揮發Κ後，34.8公克（85.7%)之3，4一雙（甲基硫）一苄基氣化物Κ棕色物質形式得到。1 Η- NMR-光譜數據（ CDC13 )與該化合物被提出的结構吻合：7.24— 7.06 ppm (S 及 d， 3 芳香性 Η) ， 3 70 ppm ( s， 2Η)， 2.47 ppm ( s - CH3 S) 5. 2.45 ppm (2s* CH3 S) 〇 21 .4. a —羥基亞胺基一3，4一雙（甲基硫）苄基氰化物根據見述於1 . 1.的方法，3 4.8公克（0 . 1 6 6莫耳）之3，4 —雙（甲基疏）一苄基氰化物與0.166莫耳亞硝酸甲酯進行反應。在翬離之後，得到23.0公克（58% )之a -羥基亞胺基-3，4一雙（甲基硫）苄基氰化物，其為棕色物質而具有熔點131 - 133C。元素分析：C 1 0 Hi 〇 N2 〇S2 ( 2 3 8.3 3 ) c m η m n m sm 計算值： 50.404.23 11.75 26.90 發現值：50.524.17 11.49 26.82 -8 7 _ 本紙張尺度逋用中國國家樣準（CNS ) A4规格（210X297公釐） ---------Lr裝------訂------線 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 A7 B7_ 五、發明説明（/yo 21.5: « — （4—甲基苯基磺醢基氧亞胺棊）一 3，4 — 二硫甲基苄基氰化物根摟 1.2所敘述的方法，10.0公克（0 . 0 4 2莫耳）之羥基亞胺基_3，4一雙（甲基硫）苄基氛化物與 8.8 公克（0.046莫耳）之對一甲苯磺酸氛化在三乙基胺的存在下進行反應。自甲苯中進行再结晶之後，得到10.5 公克（6 4%)之α - （4 一甲基苯基磺醢基氧亞胺基）—3 ，4-二硫甲基苄基氰化物，其為淡黄色结晶，具有熔點 155 — 157亡。該物質之UV光譜（乙腈）顯示一廣泛的吸收帶，其最大值在343微毫米（E= 1D710)，其延伸至476 微毫米。實施洌22: α — （甲基磺醢基氧亞胺基）一 3，4一二硫甲基苄基氰化物根據 1.2所敘述的方法，α —羥基亞胺基_3，4 一雙 (甲基硫）苄基氰化物與 6.9公克（0.06莫耳）甲烷磺醢氯進行反應。其物理數據示於表Α。實施例 23 : 9— （ 4一十二烷基苯基磺醢基氧亞胺基 )一 3，6—二（4 一羥基乙基硫）莞 -8 8 - 本紙張尺度適用中國國家梂準（CNS ) A4規格（2丨0X297公釐） I--------------IT------^ (請先閲讀背面之注意事項再填寫本頁) 經濟部中央橾隼局負工消費合作社印製 A7 B7_ 五、發明説明（r〇 23.1. 3，6—二氟蒡一 9— _ 3，6 -二氟豬 _ 9 -嗣根據 N . B a 1 a s u b r a m a n i a η 等人· 於 J. Bioorg. Med. Chen. Lett. 1991， 2，99中所敘述之多步驟合成加以製備。 23.2. 3，6—二（4 一羥基乙基硫）荛一9 一酮 10.8 公克（0.05莫耳）之3，6 -二氟菀一 9_腦， 9.4 公克（0. 12莫耳）之2-硫氫基乙酵及2 7 . 6 5公克之碳酸鉀於1 3 0毫升之N，N —二甲基乙醢胺在9 0 t進行加熱6 小時。冷卻之後，該反應混合物Μ水加以稀釋，該水性相Κ乙酸乙酯進行萃取且將該萃取物於硫酸鎂上進行乾燥。將溶劑進行揮發且該得到的黏稠狀紅色油狀物經由色層分析於矽膠（洗提劑：乙酸乙酯）上進行純化。3 . 5公克（21 % )之3，6 —二（4 一羥基乙基硫）荛一 9 —酮以橙色固體形式得到。1 H — NMR光譜與被建議的结構吻合。 23.3. 9-羥基亞胺基一 3，6—二（4—羥基乙基硫） m 4.8 公克（0.014莫耳）之3，6 -二（4 —羥基乙基硫）蒂一9-酮及2公克（0.0 2 88莫耳）之羥基氛化銨於 -8 9 - 本紙張尺度適用中國國家搮準（CNS ) Α4规格（210Χ297公釐） ---------ί ^------1Τ------.^ (請先閩讀背面之注意事項再填寫本頁) A7 ___B7_ 五、發明説明（¾) 娌流溫度下在 25 笔升之乙酵及10奄升之水進行加熱3 小時。該反懕混合物随後傾倒於冰-水内，K乙酸乙酯進行萃取並進行乾燥。經由揮發進行濃縮後，4.4公克（90 %)之9 一羥基亞胺基一3，6— 3，6—二（4 一羥基乙基硫 )荛Μ黃色固體的形式得到。1 H-!iMR光譜為與被建議的结構吻合。 23 4. 9- (4-十二烷基苯基磺醢基氧亞胺基）一 3， 6—二（4一羥基乙基硫）蓀 3.8公克（0.011莫耳）之9一羥基亞胺基一 3，6— 3 ，6—二（4 -羥基乙基硫）苐及1.67公克（0.0165莫耳 )之三乙基肢被溶解於60毫升之CH2C12且，在or：， 4 .1公克（Q.Q12莫耳）之4一十二烷基苯基磺醢氛被逐滴加入。該反應混合物在室溫進行攪拌一蝥夜且随後將得到的銨鹽濾出。於硫酸鎂上進行乾燥後，將殘餘物於矽膠 (洗提劑·•乙酸乙酯）上進行色層分析。含有紅色黏稠狀油狀物的分液被軍離出來，根據1 H— NMR光譜，其具有 9 —(4—十二烷基苯基磺醢基氧亞胺基）一3，6—二（4 一羥基乙基硫）荛之结構。元素分析：C3 s fU s N0S S3 (655.94) -90- 本紙法尺度適用中國國家橾準（CNS ) A4规格（210x297公釐） ---------/Γ^------IT------^ (請先聞讀背面之注意事項再填寫本頁) A7 B7 經濟部中央樣隼局負工消費合作社印裂五、發明説明Uj) cm Η [%] Ν [*] sm 計箄值： 64.09 6.92 2.14 14.60 發現值： 63.78 7.11 1.74 13.89 實施例 24: 3-(對一氰基一1一〔 4一十二烷基苯基磺醢基氧亞胺基]一苄基）一5，7—二丁氧基一香豆素 24.1. 3_ (對一氰基一1—[羥基亞胺基]一苄基）一 5，7—二丁氧基一香豆素 3.9公克（0.01萁耳）之3-(對一氰基苄醢基）一 5，7 —二丁氧基—香豆素（根據 D. P. Specht等人， Tetrahedron 1 98 2， 38， 1 2 Q 3進行製備）及 1. 4 公克（ 0.02 莫耳）之羥基一氛化铵於50奄升之乙酵及20毫升之水之混合物中於迴流溫度下加熱達 12小時。冷卻之後 •該反應混合物被傾倒進入冰/水，將諸相分離且並將該水相以乙酸乙酯進行萃取兩次。經過乾燥及揮發去除溶劑，得到4.4 公克之橙色祖製產物，其根據1 H- NMR，含有 3-(對一氮基一1一〔羥基亞胺基〕一苄基）一 5，7—二丁氧基一番豆素為主要產物。該粗製產物不經進一步的纯化而用於後續的步驟。 24.2. 3—(對—氰基一1 一〔4一十二烷基苯基磺醢基 -91- 本紙張尺度適用中國國家楳準（CNS ) Α4規格（210X297公釐） -------^---ί^------tr------^ (請先Η讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印製 A 7 B7 五、發明説明（你）氧亞胺基〕一苄基）一 5，7—二丁氧基一香豆素4.4 公克 (0.011莫耳）之3— （對一氰基一 1—〔羥基亞胺基〕一苄基）一 5，7—二丁氧基一香豆素，類似於實施例 1.2的製備方法，與 4.1公克（0.0118冥耳）之4一十二烷基苯基磺醯氣在 1 _ 64公克（0 . 016冥耳）之三乙基胺的存在下進行反懕。得到一非常黏稠的粗製產物，其被懸浮於己烷及乙酸乙酯中。沉澱析出的物質被濾出且將該母質液體進行揮發。 2.3公克（17%)之3—(對一氰基一 1-〔4-十二烷基苯基磺醯基氧亞胺基〕一苄基）一 5.7—二丁氧基-番豆素Μ紅色樹脂的形式得到。元素分析：C4 九 HS 〇 Ν2 07 S ( 714 . 91) cm Η [%] Ν [%] sm 計算值： 68.88 7.05 3.92 4.48 發現值： 68.69 7.96 4.28 4.55 實施例 2 5 _ 3 0 : 實施例25至30的化合物類根據1.2所敘述之方法經由Phosphorus * Sulfur »and Silicon 1993» 84, 95 were prepared. It was obtained as a pale yellow oil having a boiling point of 154 C / 22 and a yield of 29%. 21.2. 1,2—Bis (methylsulfur) —4-dichloromethyl—benzene 46 grams (0.33 mol) of A1C13 was suspended in 200 ml of 1,2-dichloroethane and At 0C, add 9.1 g (0.12 mol) of methyl dimethyl acetaldehyde. Subsequently, 17-0 g (0.1 mol) of 1,2-bis- (methylsulfur) benzene was added dropwise and the suspension was heated to room temperature. When the starting material is no longer detectable by GC analysis, the solvent is poured into ice / water and the organic phase is separated and dried over magnesium sulfate. When the solvent had been removed by evaporation, 12.1 g (55%) of 1,2-bis (methylsulfide) -4-aminomethyl-benzene K was obtained as a yellow oil. The 1H-NMR spectrum (CDC13) of this compound agrees with the proposed structure: 7. 17-7.13, s and d, 3 aromatic fluorene; 452, s, 2H; 2.44, s, CH3 S and 2.43, s , CH3 S. 21.3. 3,4-Bis (methylthio) benzyl cyanide 42.5 g (0.194 hare) of 1,2-bis (methylsulfur) -4 monohydromethyl monobenzene and 25.3 g (0.388 mole) The potassium cyanide is stirred at 20 (1 ml of DMS0 at ambient temperature. When the starting material is no longer -8 6 _ This paper size applies to China National Standard (CNS) A4 (210X297 mm) --- ------ Installation ------ Order ------ line (please read the notes on the back before filling in this I) The Central Bureau of Standards of the Ministry of Economy Shellfish consumer cooperation Du printed A7 _B7_ V. Description of the invention (fj) When detected by GC analysis, the brown solution was poured into ice / water and extracted with ethyl acetate and the organic phase was dried over magnesium sulfate. After encountering volatile K, 34.8 g (85.7%) ) Of 3,4-bis (methylsulfide) -benzyl gaseous substance K as a brown material. 1 Η-NMR-spectral data (CDC13) agrees with the proposed structure of the compound: 7.24—7.06 ppm (S and d , 3 aromatic Η), 3 70 ppm (s, 2Η), 2.47 ppm (s-CH3 S) 5. 2.45 ppm (2s * CH3 S) 〇21 .4. A —hydroxyimine group 3,4— Bis (methylsulfur Benzyl cyanide according to the method described in 1.1, 3 4.8 g (0.16 mol) of 3,4-bis (methylsulfo) -benzyl cyanide and 0.166 molar nitrite The ester is reacted. After deaeration, 23.0 g (58%) of a-hydroxyimino-3,4-bis (methylthio) benzyl cyanide are obtained, which is a brown substance with a melting point of 131-133C. Elemental analysis: C 1 0 Hi 〇N2 〇S2 (2 3 8.3 3) cm η mnm sm Calculated value: 50.404.23 11.75 26.90 Found value: 50.524.17 11.49 26.82 -8 7 _ This paper uses the Chinese national standard (CNS) A4 specification (210X297 mm) --------- Lr equipment -------- Order ------ Line (Please read the precautions on the back before filling this page) Ministry of Economic Affairs Printed by the Central Bureau of Standards Shellfish Consumer Cooperative A7 B7_ 5. Description of the invention (/ yo 21.5: «— (4-methylphenylsulfonyloxyimine 棊)-3,4-dithiomethylbenzyl cyanide According to the method described in 1.2, 10.0 g (0.042 mol) of hydroxyimino_3,4-bis (methylthio) benzyl odorant and 8.8 g (0.046 mol) of one to one Toluenesulfonic acid aeration The reaction is performed in the presence of triethylamine. After recrystallization from toluene, 10.5 g (64%) of α- (4-methylphenylsulfonyloxyimino) -3,4-dithiomethylbenzyl cyanide was obtained. Light yellow crystal with melting point 155-157 die. The substance's UV spectrum (acetonitrile) shows a broad absorption band with a maximum of 343 μm (E = 1D710) and an extension to 476 μm. Implementation 洌 22: α- (methylsulfonyloxyimino) -3,4-dithiomethylbenzyl cyanide According to the method described in 1.2, α-hydroxyimino_3,4-bis ( Methylthio) benzyl cyanide was reacted with 6.9 g (0.06 mol) of methanesulfonyl chloride. The physical data are shown in Table A. Example 23: 9— (4-dodecylphenylsulfonyloxyimino) —3,6-di (4-hydroxyethylsulfuryl) —Wan-8 8-This paper is in accordance with China's national standards (CNS) A4 specification (2 丨 0X297mm) I -------------- IT ------ ^ (Please read the notes on the back before filling this page) Ministry of Economy Printed by the Central Bureau of Work and Consumer Cooperatives A7 B7_ V. Description of the invention (r〇23.1. 3, 6-difluorofluorene 9- _ 3, 6-difluoro pig _ 9-嗣 according to N. B a 1 asubramania η et al. Prepared by the multi-step synthesis described in J. Bioorg. Med. Chen. Lett. 1991, 2, 99. 23.2. 3,6-bis (4-hydroxyethylthio) fluorene-9-one 10.8 grams (0.05 moles) of 3,6-difluorofluorene-9 brain, 9.4 grams (0.12 moles) of 2-thiohydroacetone and 27.6.5 grams of potassium carbonate in 1 3 0 ml of N, N-dimethylacetamide was heated at 90 t for 6 hours. After cooling, the reaction mixture was diluted with water, the aqueous phase was extracted with ethyl acetate and the extract was extracted with magnesium sulfate. The solvent was evaporated and The obtained viscous red oil was purified by chromatography on silica gel (eluent: ethyl acetate). 3.5 g (21%) of 3,6-bis (4-hydroxyethylsulfur) 荛The 9-one was obtained as an orange solid. The 1 H-NMR spectrum was consistent with the proposed structure. 23.3. 9-Hydroxyimino-3,6-bis (4-hydroxyethylsulfur) m 4.8 g (0.014 mol) Ear) 3,6-di (4-hydroxyethylsulfur) di-9-one and 2 g (0.0 2 88 mole) of hydroxyaminated ammonium at -8 9-This paper size applies to Chinese national standards ( CNS) Α4 specifications (210 × 297 mm) --------- ί ^ ------ 1Τ ------. ^ (Please read the notes on the back before filling this page) A7 ___B7_ V. Description of the invention (¾) Heat at 25 liters of acetic acid and 10 liters of water for 3 hours at reflux temperature. The reaction mixture is then poured into ice-water, K ethyl acetate is extracted and After drying, it was concentrated by volatilization, and 4.4 g (90%) of 9-hydroxyimino-3,6--3,6-bis (4-hydroxyethylsulfur) was obtained as a yellow solid. 1 H -! iMR spectrum Consistent with the proposed structure. 23 4. 9- (4-Dodecylphenylsulfonyloxyimino)-3, 6-bis (4-hydroxyethylsulfide) 3.8 g (0.011 mole) ) Of 9-hydroxyimino-3,6-3,6-bis (4-hydroxyethylthio) fluorene and 1.67 g (0.0165 mole) of triethyl limb were dissolved in 60 ml of CH2C12 and, in or :, 4.1 grams (Q.Q12 mole) of 4-dodecylphenylsulfonium is added dropwise. The reaction mixture was stirred at room temperature overnight and then the obtained ammonium salt was filtered off. After drying over magnesium sulfate, the residue was subjected to chromatography on a silica gel (eluent · • ethyl acetate). The liquid containing red viscous oil was separated. According to 1 H-NMR spectrum, it had 9- (4-dodecylphenylsulfonyloxyimino)-3,6-bis ( 4 Structure of monohydroxyethyl sulfide) hydrazone. Elemental analysis: C3 s fU s N0S S3 (655.94) -90- The paper method scale is applicable to China National Standard (CNS) A4 specification (210x297 mm) --------- / Γ ^ ----- -IT ------ ^ (Please read the precautions on the back before filling out this page) A7 B7 Printed by the Consumer Sample Cooperatives of the Central Samples Bureau of the Ministry of Economic Affairs 5. Description of the invention Uj) cm Η [%] Ν [ *] sm calculated value: 64.09 6.92 2.14 14.60 Found value: 63.78 7.11 1.74 13.89 Example 24: 3- (p-cyano-1 1- [4-dodecylphenylsulfonyloxyimino]- Benzyl) -5,7-dibutoxy-coumarin 24.1. 3_ (p-cyano-1- [hydroxyimino] -benzyl) 5,7-dibutoxy-coumarin 3.9 g (0.01 萁) of 3- (p-cyanobenzylfluorenyl) -5,7-dibutoxy-coumarin (according to DP Specht et al., Tetrahedron 1 98 2, 38, 1 2 Q 3 Prepared) and 1.4 g (0.02 mol) of hydroxy-aerated ammonium were heated in a mixture of 50 liters of acetic acid and 20 ml of water at reflux temperature for 12 hours. After cooling • The reaction mixture was poured into ice / water, the phases were separated and the aqueous phase was extracted twice with ethyl acetate. The solvent was removed by drying and volatilization to obtain 4.4 g of an orange ancestral product, which, according to 1 H-NMR, contained 3- (p-nitrozyl-1 [[hydroxyimino] -benzyl) -5,7-2 The main product is butoxymonomycin. This crude product was used in subsequent steps without further purification. 24.2. 3— (p-cyano-1 1- [4-dodecylphenylsulfonyl-91-)-This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) ----- -^ --- ί ^ ------ tr ------ ^ (Please read the notes on the back before filling out this page) Printed by Shellfish Consumer Cooperative, Central Standards Bureau, Ministry of Economic Affairs A 7 B7 V. Description of the invention (You) oxyimino] -benzyl) -5,7-dibutoxy-coumarin 4.4 g (0.011 mole) Amine] -benzyl) -5,7-dibutoxy-coumarin, similar to the preparation method of Example 1.2, and 4.1 g (0.0118 glutamine) of 4-dodecylphenylsulfonium The reaction was carried out in the presence of 1-64 g (0.016 hare) of triethylamine. A very viscous crude product was obtained, which was suspended in hexane and ethyl acetate. The precipitated material was filtered off and the mother liquid was evaporated. 2.3 g (17%) of 3- (p-cyano-1- [4-dodecylphenylsulfonyloxyimino] -benzyl) -5.7-dibutoxy-myristotin M Get in the form of red resin. Elemental analysis: C4 Nine HS 〇2 07 S (714.91) cm Η [%] Ν [%] sm Calculated value: 68.88 7.05 3.92 4.48 Found value: 68.69 7.96 4.28 4.55 Example 2 5 _ 30: Example 25 Compounds of 30 to 30 are processed according to the method described in 1.2

將相對懕的反應物進行反應而得。结構及物理數據示於表A 〇 -92- 本紙張尺度適用中國國家橾率（CNS ) A4it格（210X297公釐） --------rr^------IT------ (請先閲讀背面之注意事項再填寫本頁) 五、發明説明（β )It is obtained by reacting a relatively tritium reactant. The structure and physical data are shown in Table A. 〇-92- This paper size is applicable to China National Standard (CNS) A4it grid (210X297 mm) -------- rr ^ ------ IT-- --- (Please read the notes on the back before filling out this page) 5. Description of the invention (β)

表 A 0 A7 B7 R,Table A 0 A7 B7 R,

Ri Ι?2 fe _/ m 18 Clfe 0 Clfe 0 35¾ W^¥b, rap. 149-151t：(分解）Ri Ι? 2 fe _ / m 18 Clfe 0 Clfe 0 35¾ W ^ ¥ b, rap. 149-151t: (decomposed)

22 Clfe S Clfe S MSB晶， Clfe 74% mp. 164-165C ------IT------緣 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印裝 25 Clfe 0 Clfe 022 Clfe S Clfe S MSB crystal, Clfe 74% mp. 164-165C ------ IT ------ Fate (Please read the precautions on the back before filling this page) Staff Consumption of the Central Standards Bureau of the Ministry of Economic Affairs Cooperative printed 25 Clfe 0 Clfe 0

-ch3 结晶 h,c 69¾ mp. 149-152 -93- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）五、發明説明 {J〇) 26 Clfe S Clfe Ο 27 Cife S (¾ 28 Cife 5-ch3 Crystal h, c 69¾ mp. 149-152 -93- This paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) 5. Description of the invention {J〇) 26 Clfe S Clfe 〇 27 Cife S (¾ 28 Cife 5

Ri R2Ri R2

29 Clfe S H A7 B7 52% πρ. 139-142 Ό 晶 nip. 162-164 Ό29 Clfe S H A7 B7 52% πρ. 139-142 晶 Crystal nip. 162-164 Ό

Clfe 62% cf, 4 30¾ mp. 162-164 Ό mj m ---------Vi ------IT------0 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局貝工消費合作社印装Clfe 62% cf, 4 30¾ mp. 162-164 Ό mj m --------- Vi ------ IT ------ 0 (Please read the precautions on the back before filling in this Page) Printed by Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs

30 Cife S H -94- -o-«结晶， ip. 167-168*0 (細本紙張XJt適用中國國家標準（CNS ) A4規格（21OX297公釐）經濟部中央標準局員工消费合作社印«. A7 B7_ 五、發明説明（f/) 33% 结晶， BP. 160-165^ 實施例31:光阻物質的製備一阻抗物質溶液經由將 65 份之聚乙烯基酚（Mw = 22 000 Polyscience) 30份之陸（甲氧基甲基）三聚氰胺（Cymel® 303， Cyanamide)及5份的受試化合物加 K混合而進行製備並將2.5 公克之此溫合物溶解於含有 1 0 0 0 ppm之流動助劑（FC 4 3 0 )之7.5公克之乙酸1-甲氧基-2 -丙基酯中。該溶疲經由5000 rev/rain之自旋被覆30秒施用於直徑10.2公分（4吋）之矽晶元之光亮的及以六甲基二矽·氮烷（disilazane) —處理的一面。此造成厚度1微米的被覆。溶劑經由將該被覆晶元置於—加熱板上於no υ進行乾燥60秒而予K去除。因此得到的檢體經由具不同灰階區域之光罩進行逐橡輻射，其使用干擾濾光片而選擇性地讓波長3 6 5微毫米，405微牽米或4 3 6微毫米的光（Canon PLA 501，水銀高壓燈）通過。該晶元随後於 110Ό加熱60秒以達成被輻射區域的交叉聯结’其係由輻射後釋出的酸進行催化。顯影随後在一 2. 8%四甲基銨氫氧化物的溶疲中進行60秒。決定需要達成與顗影前薄層厚 -95- 本紙張尺度適用中國國家揉準（CNS ) A4規格（210X297公釐） ---------.ί ^------1Τ------it (請先閲讀背面之注意事項再填寫本頁) A7 B7 五、發明説明（經濟部中央標準局員工消費合作社印裝度相藺之顯影後薄層厚度的辐射劑量。薄層厚度的测量使用 Zeiss Axiotron (白光干擾性）進行。需要的辐射劑量愈低，該沉潛性光硬化麵的反應性愈佳。结果示於表】。结果顯示根據本發明使用光硬化劑類’ 得到的負性阻抗物具有高度的敏感性 0 表1 光硬化劑在 3 6 5微牽米薄層所來自的的敏感度厚度買施例 [mJ/cb2 ] [ηπ ] 1 10 1090 2 ( E / Z混合物） <6 1080 光硬化劑在 3 6 5微牽米薄層所來自的的敏感度厚度實施例 [mJ/cm2 ] [m ] 2 ( Z異構物） 10 1080 3 < 6 1100 96- I--------f ^------.W------i (請先Μ讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家揉準（CNS ) A4規格（210X297公釐）經濟部中央標準局貝工消費合作社印装 A7 _B7____ 五、發明説明（7 >) 4 <6 1100 經由Μ波長405微毫米或436微毫米的光進行摇射’亦同漾得到影像。實施例32:正性阻抗物質的製備 a)膠黏劑聚合物的製備經由類似於 K. Nakano等人， Proc. SPIE， 2438， 433—39 (1995): terpolyeers of methacrylic acid tetrahydrο — 2Η— pyranyl ester ， methacrylic acid and methyl methacrylate而完成 0 在一250 毫升容積之圓底錐形瓶，將8.51公克（50 毫莫耳）之甲基丙烯酸四氫一2H-at哺基酯，4.Q公克（ 40 奄莫耳）之甲基丙烯酸甲酯，0.86公克（10毫莫耳 )之甲基丙烯酸及 0.3 2公克之叠氮一雙異丁醢腈於 100 毫升之四氫呋喃中所形成的溶液在75t：於氮氣環境下進行攪拌20個小時。將該反應溶液冷卻且隨後自1 公升的η-己烷中沉澱析出。形成的沉澱物被濾出並於一高度真空的環境下進行乾燥（4X 1 0 - s巴），得到11 . 4公克（85%理論產率）之白色粉末。 -97- 本紙張尺度適用中國國家榡準（CNS ) A4%格（210X297公釐） ---------------tT------^ (請先閲讀背面之注意事項再填寫本頁) 妙妙經濟部中央標準局貝工消费合作社印製 A7 ___B7 _ 五、發明説明（fp GPC (聚苯乙烯校正）：Μη = 7，100， Mw = 19 ，500 ， PD = 2.7 TGA (ίου/分鐘）：介於110-2101C間重量損失32 % b)正性i-線阻抗物質的製備一阻抗物質溶疲經由將0.98公克之來自製備實施例a )之聚合物及 20牽克之來自實施例3之光硬化劑溶解於4 公克之乙酸1-甲氧基- 2 —丙基酯而製成。該溶疲經由 3 0 0 0 rev/ min進行自旋被覆施用至具有直徑7.65公分 (3 吋）的矽晶元。接著在ιοου進行乾燥1分鐘而得到具有被覆厚度1.0微米的薄層。該薄層使用一 Ushio UXM -5Q2 MD型水銀蒸氣燈》經由一窄頻帶干擾«鏡及一鉻/ 石英光罩，在36 5微毫米及以5mJ/ cm2劑量進行逐像輻射。該晶元随後於加熱板上於100Ό進行加熱1分中且随後在 0.033N四甲基銨氫氧化物於水中形成的溶疲中進行顯影，阻抗物質薄層先前被輻射的區域溶解，但是無輻射區域仍存在。得到的光罩的正性型態具有良好的解析度。實施例33 : -9 8 ~ 本紙張A度適用中國國家標準（CNS ) A4%格（210X29*7公釐） ----------裝------訂------壤 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央榡準局員工消費合作社印策 A7 B7 五、發明説明（7ί) 一阻抗物質溶液經由將65份之聚乙烯基酚（Mw = 5 000，Maruzen Chemicals) * 30 份之陸（甲氧基甲基）三聚氰胺（Cynel®303， Cyanamiile)及5份的受試化合物加K混合而進行製備並將2.5 公克之此混合物溶解於含有1 0 0 0 ppm之流動助劑（FC 4 3 0，3M公司）之7.5公克之乙酸1-甲氧基一 2—丙基酯中。該溶疲经由 5 0 0 0 rev/ min之自旋被覆30秒施用於直徑10.2公分（4时）之矽晶元之光亮的及以六甲基二矽氮烷（disilazane) —處理的一面。此造成厚度1徹米的被覆。溶劑经由將該被覆晶元置於一加熱板上於 llOt：進行乾煉6 0秒而予以去除。因此得到的檢體經由具不同灰階區域之光罩進行逐橡輻射，其使用干擾漶光片而選擇性地讓波長 3 6 5微毫米，4 0 5微毫米或436微毫米的光（Canon PLA 501>.水銀高壓燈）通過。該晶元随後於110 =加熱60秒以達成被輻射區域的交叉聯结，其係由轜射後釋出的酸進行催化。顯影随後在一 2.8 %四甲基銨氫氧化物的溶液中進行60秒。決定需要達成與顯影前薄層厚度相關之顯影後薄層厚度的輻射劑量。薄層厚度的測量使用 Zeiss Axiotron (白光干擾性）進行。需要的輻射劑量愈低，該沉潛性光硬化劑的反應性愈佳。结果示於表2。结果顯示根據本發明使用光硬化劑類，得到的負性阻抗物具有高度的敏感性。本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐） ----------‘f^------tl------.^ (請先閲讀背面之注意事項再填寫本頁) A7 B7 五、發明説明（^ ) 光硬化劑在3 6 5微毫米薄層所來自的的敏感度厚度實施例 C mJ/ cm2 ] [nm] 15 5 960 16 7 995 經由Μ波長 405微毫米或4 3 6微毫米的光進行輻射，亦同樣得到影像。以實施例11及17的化合物在相關之波長亦得到影像。 --------ί^.------IT------0 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印裝 -10 0- 本紙张尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）30 Cife SH -94- -o- «Crystal, ip. 167-168 * 0 (thin paper XJt applies Chinese National Standard (CNS) A4 specification (21OX297 mm) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs«. A7 B7_ V. Description of the invention (f /) 33% crystalline, BP. 160-165 ^ Example 31: Preparation of a photoresist substance A solution of resistive substance is obtained by passing 65 parts of polyvinylphenol (Mw = 22 000 Polyscience) 30 parts Zhilu (methoxymethyl) melamine (Cymel® 303, Cyanamide) and 5 parts of the test compound were mixed with K to prepare and dissolved 2.5 g of this warm compound in a flow aid containing 1000 ppm Agent (FC 4 3 0) in 7.5 grams of 1-methoxy-2-propyl acetate. The solution was applied to a silicon diameter of 10.2 cm (4 inches) by spin coating at 5000 rev / rain for 30 seconds. The bright side of the wafer and treated with hexamethyldisilazane. This results in a coating thickness of 1 micron. The solvent is dried by placing the coated wafer on a hot plate at no υ 60 K is removed in seconds. Therefore, the obtained specimen is irradiated by rubber through a mask with different gray scale regions. A light filter (Canon PLA 501, mercury high-pressure lamp) with a wavelength of 36.5 micrometers, 405 micrometers, or 4 3 6 micrometers was selectively passed through an interference filter. The wafer was then heated at 110 ° for 60 seconds. In order to achieve the cross-linking of the irradiated area, it is catalyzed by the acid released after irradiation. Development is then carried out in a dissolution of 2.8% tetramethylammonium hydroxide for 60 seconds. Thin film thickness before shadow -95- This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) ---------. Ί ^ ------ 1Τ ---- --it (Please read the precautions on the back before filling this page) A7 B7 V. Description of the invention (The radiation dose of the thin layer thickness after development is comparable to the printed degree of the staff consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The measurement was performed using Zeiss Axiotron (white light interference). The lower the required radiation dose, the better the reactivity of the latent light-hardened surface. The results are shown in the table. The results show that using the light hardeners according to the present invention, the negative Sexual impedance has a high sensitivity 0 Table 1 Light hardener at 3 6 5 Sensitivity thickness of the layer from which to buy the example [mJ / cb2] [ηπ] 1 10 1090 2 (E / Z mixture) < 6 1080 Sensitivity of the light hardener from 3 6 5 Degree Thickness Example [mJ / cm2] [m] 2 (Z isomer) 10 1080 3 < 6 1100 96- I -------- f ^ ------. W --- --- i (Please read the notes on the back before filling in this page) This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) Printed by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 _B7____ 5 7. Description of the invention (7 >) 4 < 6 1100 The image is obtained by panning through light having an M wavelength of 405 micrometers or 436 micrometers. Example 32: Preparation of a positive impedance material a) Preparation of an adhesive polymer via a method similar to K. Nakano et al., Proc. SPIE, 2438, 433-39 (1995): terpolyeers of methacrylic acid tetrahydrο — 2Η — pyranyl ester, methacrylic acid and methyl methacrylate to complete 0. In a 250 ml volume round-bottom conical flask, 8.51 g (50 mmol) of tetrahydro-2H-at methacrylate, 4.Q g ( 40 mol) of methyl methacrylate, 0.86 g (10 mmol) of methacrylic acid and 0.3 2 g of azide-bisisobutyronitrile in 100 ml of tetrahydrofuran at 75t: Stir under nitrogen for 20 hours. The reaction solution was cooled and then precipitated from 1 liter of η-hexane. The formed precipitate was filtered off and dried under a high vacuum (4 × 10-s bar) to obtain 11.4 g (85% of theoretical yield) of a white powder. -97- This paper size applies to China National Standard (CNS) A4% grid (210X297mm) --------------- tT ------ ^ (Please read the back first Please pay attention to this page and fill in this page again.) Printed by the Miao Miao Miao Miao Economic Central Standards Bureau Shellfish Consumer Cooperative A7 ___B7 _ V. Description of the invention (fp GPC (polystyrene correction): Μη = 7,100, Mw = 19,500, PD = 2.7 TGA (ίου / minute): 32% weight loss between 110-2101C b) Preparation of positive i-line resistance material-resistance material is dissolved by passing 0.98 g of polymer from preparation example a) And 20 grams of the light hardener from Example 3 was prepared by dissolving 4 grams of 1-methoxy-2-propyl acetate. The solution was spin-coated to a silicon wafer having a diameter of 7.65 cm (3 inches) via 3 000 rev / min. Then, it was dried at ιοου for 1 minute to obtain a thin layer having a coating thickness of 1.0 m. The thin layer uses a Ushio UXM -5Q2 MD type mercury vapor lamp through a narrow band interference mirror and a chrome / quartz mask to perform image-by-image radiation at 36 5 μm and 5 mJ / cm2 dose. The wafer is then heated on a hot plate at 100 ° F for 1 minute and then developed in a solution of 0.033N tetramethylammonium hydroxide in water. The previously irradiated area of the thin layer of resistive material is dissolved, But radiation-free areas still exist. The positive shape of the obtained photomask has good resolution. Example 33: -9 8 ~ A paper of this paper conforms to Chinese National Standard (CNS) A4% grid (210X29 * 7 mm) ---------- installation ------ order --- --- Soil (please read the precautions on the back before filling this page) Employees' Cooperatives Cooperative Policy A7 B7, Ministry of Economic Affairs, Central Government of the People's Republic of China V. Description of the Invention (7ί) A solution of resistive substance passes 65 parts of polyvinylphenol (Mw = 5 000, Maruzen Chemicals) * 30 parts of land (methoxymethyl) melamine (Cynel® 303, Cyanamiile) and 5 parts of the test compound were added with K to prepare and 2.5 g of this mixture was dissolved In 7.5 grams of 1-methoxyacetic acid 2-propyl ester containing 10,000 ppm of flow aid (FC 4 30, 3M). The solution was applied to the bright side of the silicon wafer with a diameter of 10.2 cm (4 o'clock) and treated with hexamethyldisilazane—a spin coating of 50 000 rev / min for 30 seconds. This results in a coating thickness of 1 metre. The solvent was removed by placing the coated wafer on a hot plate at 110 ° C .: dry refining for 60 seconds. The specimens thus obtained are irradiated through a mask with different grayscale areas, which use interference chirps to selectively allow light with a wavelength of 36.5 micrometers, 40 micrometers or 436 micrometers (Canon PLA 501 >. Mercury high pressure lamp) passed. The wafer is then heated at 110 = 60 seconds to achieve cross-linking of the irradiated area, which is catalyzed by the acid released after the emission. Development was then performed in a 2.8% solution of tetramethylammonium hydroxide for 60 seconds. Decide on the radiation dose needed to achieve the thickness of the thin layer after development in relation to the thickness of the thin layer before development. Thin layer thickness was measured using Zeiss Axiotron (white light interference). The lower the required radiation dose, the better the reactivity of the latent light hardener. The results are shown in Table 2. The results show that the use of photohardeners according to the present invention results in a highly negative resistive material. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) ---------- 'f ^ ------ tl ------. ^ (Please read the back first Please note this page and fill in this page again) A7 B7 V. Description of the invention (^) Sensitivity thickness of the light hardener in the thin layer of 3 65 micrometers Example C mJ / cm2] [nm] 15 5 960 16 7 995 is also irradiated with light having an M wavelength of 405 micrometers or 436 micrometers, and an image is also obtained. Images were also obtained with the compounds of Examples 11 and 17 at the relevant wavelengths. -------- ί ^ .------ IT ------ 0 (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs-10 0- This paper size applies to China National Standard (CNS) A4 (210X 297mm)

Claims

1六、申請專利範圍 A8 B8 C8 D816.Scope of patent application A8 B8 C8 D8

1. 一種可光活化的光阻組成物，其包括 a)至少一種化合物，其可於酸的作用下被交叉聯结及 /或須請委Μ明示，本案修正後是否變更康實"?内 b) 至少一種化合物，其溶解度在酸的作用下被改變及 c) 作為光起動劑之至少一種式I之化合物，其在成份 (a)及（b)的重量當作100 3：時，佔1至15¾重量， R； 0 II -C- -C = N-0-S0，- I 2 R, 其中a為0且X為1 ; (請先閲讀背面之注意事項本頁) —f ml i·—— n^i i i a^—·- nf n! m· n ^ m· ml ^^1 In 訂 R, (I) 經濟部中央標準扃月工消费合作社印装 Rt為苯基，其經由一種或多種自由基加以取代，該自由基可為 Ci-Ctz烷基，苯基，OR 4 * SR4及/或 NR5R6 ，其條件為當該苯環經由甲氧基進行取代時，在該環上至少出現一個進一步之取代基•或 Ri為萘基，匾基或菲基；自由基蔡基，憩基及菲基為未經取代的或經由 Ci -C6烷基，苯基， 0R4 ， SR4及/或經由NRs IU 本紙張尺度適用中國國家揉率（CNS ) Α4規格（210x297公釐） 1六、申請專利範圍 A8 B8 C8 D81. A photoactivatable photoresist composition, comprising a) at least one compound, which can be cross-linked under the action of an acid and / or must be explicitly stated by the committee. Is the Kangshi changed after the amendment? Inside b) at least one compound whose solubility is changed by the action of an acid and c) at least one compound of the formula I as a light starter, whose weight of ingredients (a) and (b) is taken as 100 3: 1 to 15¾ weight, R; 0 II -C- -C = N-0-S0,-I 2 R, where a is 0 and X is 1; (Please read the precautions on the back page first) —f ml i · —— n ^ iiia ^ — ·-nf n! m · n ^ m · ml ^^ 1 In Order R, (I) Central Standard of the Ministry of Economic Affairs 扃 Monthly Industrial Cooperative Cooperative Printing Rt is phenyl, which is Or more than one radical is substituted, the radical may be Ci-Ctz alkyl, phenyl, OR 4 * SR4 and / or NR5R6, provided that when the benzene ring is substituted by a methoxy group, at least on the ring A further substituent group appears • or Ri is naphthyl, plaque or phenanthryl; radical Zeidyl, aryl and phenanthryl are unsubstituted or via Ci-C6 alkyl, phenyl, 0R4, SR4 and / or NRs IU This paper size is applicable to China National Kneading Ratio (CNS) A4 specification (210x297 mm) 16. Application scope A8 B8 C8 D8

1. 一種可光活化的光阻組成物，其包括 a)至少一種化合物，其可於酸的作用下被交叉聯结及 /或須請委Μ明示，本案修正後是否變更康實"?内 b) 至少一種化合物，其溶解度在酸的作用下被改變及 c) 作為光起動劑之至少一種式I之化合物，其在成份 (a)及（b)的重量當作100 3：時，佔1至15¾重量， R； 0 II -C- -C = N-0-S0，- I 2 R, 其中a為0且X為1 ; (請先閲讀背面之注意事項本頁) —f ml i·—— n^i i i a^—·- nf n! m· n ^ m· ml ^^1 In 訂 R, (I) 經濟部中央標準扃月工消费合作社印装 Rt為苯基，其經由一種或多種自由基加以取代，該自由基可為 Ci-Ctz烷基，苯基，OR 4 * SR4及/或 NR5R6 ，其條件為當該苯環經由甲氧基進行取代時，在該環上至少出現一個進一步之取代基•或 Ri為萘基，匾基或菲基；自由基蔡基，憩基及菲基為未經取代的或經由 Ci -C6烷基，苯基， 0R4 ， SR4及/或經由NRs IU 本紙張尺度適用中國國家揉率（CNS ) Α4規格（210x297公釐） A8 B8 C8 D8 六、申請專利範圍加κ取代；或為一雜芳基自由基，其為未經取代的或經由 Ci-Ce烷基，0R4 ，SR4及/或經由NRsR6M K取代，其條件為Ri不為未經取代的噻嗯基； ϋζ為未經取代的或CN -取代之苯基，C2 — Cs烷氧基羰基，CN ;或 Ri及 R2形成一 5—或6—員環，其為未經取代的或經由Ct-Cs烷基，0R4 ， SR4或經由NRslU加Μ取代且一種或多種苯並自由基可與其稠合； it- ，當X為1時，為Ci — Cl 8烧基，Cl —C4齒烧基或苯基，自由基苯基可為未經取代的或經由一個或多個自由基取代，該等自由基為鹵素，Ci _C4鹵烷基， CN ，NO 2 * C i - C t β 烷基，苯基，OR 4 ; 經濟部中央揉準局員工消费合作社印袋 (請先閲讀背面之注意事項再本頁) R4為氫， Ct -Ci z烷基，其為未锂取代的或經由〇 Η，加K取代； Rs及Rs彼此獨立為氳或“ 一Ci 2烷基。 2.根據申請專利範团第1項的光阻組成物，其中在式j 之化合物中，IU為苯基，其經由^一％烷基，〇R4 -2- 本紙張尺度適用中國國家揉準（CNS ) Λ4规格（210X297公釐）經濟部中央標準局只工消费合作社印裝 A8 B8 C8 D8 六、申請專利範圍，S1U及/或經由NRs Rs加K取代。 3. 根據申請專利範圍第1項的光阻組成物，其中在式I 之化合物中，為一雜芳基自由基，其為未經取代的或經由Ct -Cs烷基，01U ， SR4及/或經由NRS 進行單一一或多一取代。 4. 根據申請專利範圍第1項的光阻組成物，其中在式I 之化合物中，R2為CN 〇 5. 根據申請專利範圃第1項的光阻組成物，其中在式I 之化合物中，R4為（^ 一（：6烷基，其為未經取代的或經由 Ο Η基進行取代。 6. 根據申請專利範圍第1項的光阻组成物，其中在式I 之化合物中，Rs為“ 一Ct a烷基，Cr — (U鹵烧基，或苯基，其為未經取代的或經由鹵素，N〇2 ，Ci 一（：4鹵烷基，Ci— Cl2烷基，〇R4進行取代。 7·根據申請專利範圍第1項的光阻組成物，其中在式I 之化合物中，b為0且又為 1，Ri為3，4一二甲氧基苯基， 3，4一二（甲基硫）苯基，3—甲氣基一 4 —甲基硫苯基或4 一甲基醗苯基，R2為CN或4 -氰基苯基，且R3為苯基 -3 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先《讀背面之注意事項再Ϊ本頁) 訂 '^! 經濟部中央標準局負工消费合作社印装 A8 B$ C8 D8 六、申請專利範圍，4 一甲基苯基，4 一甲氧基苯基，3—三氟甲基苯基，4 — 氛苯基，甲基，異丙基，η -辛基，2，4，6—(三異丙基 )一苯基4 一硝基苯基，2，4，6—三甲基苯基或4 —十二烷基苯基，或Ri及R2共同形成一莽系統，其中該芳香環經由甲氧基或羥基乙基硫基匾加K取代。 8. 根據申請專利範圍第1項的光咀组成物，其進一步包括成份c) Μ外之進一步的光起動劑類，敏感劑類及/ 或添加物類，其中該等光啟動劑係選自包括自.由基光啟動劑之一群姐，這些自由基光啟動劑來自二苯嗣類，苯乙嗣衍生物類，？Dec —羥基環烷基苯基嗣，二烷氧基苯乙画， a —經基一或a —肢基一苯乙嗣，4 一芳醢基一 1，3 —二氧伍環類，安息香（benzoin)烷基醚類及苯偶醢（benzil) 醛類，或選自單醢基膦氧化物類，雙醣基膦氧化物類， titanocenes，三鹵甲基三嗪衍生物類，六芳基雙眯唑基化合物類，陽離子光啟動劑類，過氧化合物類，芳香性磺鉻或碘鎗塩類，或環戊二烯基一芳烴一鐵（I)錯合塩類。 9. 根據申請專利範圍第1項的組成物，其用於製備印刷板類，色彩過濾物類，阻抗材料類及作為影像記錄性材料。 10 . —種式lb之化合物 -4- 本紙張尺度適用中國國家揉準（CNS ) A4洗格（210X297公釐） (請先閲讀背面之注項再Ϊ本頁) 訂 39209¾申請專利範圍 A8 B8 C8 D8 0 R，T: •C = N~〇-SO^ I 4R, •FU (lb) 其中Dl為0且 X為1 ; .(請先Η讀背面之注意事項再Wr本頁) 經濟部中央橾準局男工消費合作社印製 "為苯基或萘基，其經由自由基可為Ci — Cs烷基，苯基，0R4 ，SR4及/或NR S Re單一或多取代；或 Ri 〃為匾基或菲基；自由基憩基及菲基為未經取代的或經由Cl — Cs烷基，苯基，〇R4 ，SR4及/或經由HRs Re加K里--或多重一取代，其條件為若” 為經0R4 取代之苯S時，至少一個另外的取代基SR4或NRS Rs存在 ;或為一雜芳基自由基，其為未經取代的或經由 Ci 一 C6烷基，〇R4 ， SR4及/或經由NRs Re加K取代，其條件為Ri 〃不為未取代的睡嗯基或呋哺基； Rz為未經取代的苯基， C2 — Ce烷氣基羰基，或CN ; -5 - 本紙張尺度逋用中國國家標準（CNS ) A4規格（210X297公釐）訂 -¾ A8 B8 392092_ξ\ 六、申請專利範圍或^ "及Rz形成一 5—或員環，其為未經取代的或經由Ci — Cs焼基OR4 ’ SR4或經由NRs Re加K 取代且一種或多種苯並自由基可與其稠合； R3 ，當X為1時，為Ct—CiS烷基 Cl 一 C4鹵烷基或苯基，蔡基；自由基苯基為未經取代的或绶由一種或多種鹵素，Ci _C4鹵烷基，CN，N〇2 ，C支-Ci s烷基或 0 R 4加Μ取代； lU為氫， Ct 一“ z烷基，其為未經取代的或鍟由 0 Η加K取代； R5及Re彼此獨立為氫或“ -Ct 2烷基。經濟部中央揉準局具工消費合作社印I (請先閲讀背面之注意事項再ί本頁) 11.根據申請專利範圍第10項的化合物，其即為α_ ( 甲基磺醢基氧亞胺基）一3，4一二甲氧基一苄基氰化物， α_ (4—十二烷基苯基磺醯基氧亞胺基）一 3，4_二甲氧基苄基氰化物或α— （4一甲基一苯基磺醢基氧亞胺基）— 4一硫甲基苄基氰化物，α_ (2—丙基磺醢基氧亞胺基） —3，4一二甲氧基苄基氰化物，〇( — （苯基磺醢基氣亞胺基）一3，4一二甲氧基苄基氰化物，α_ (4 —甲氧基苯基 -6 - 本紙張尺度逋用中國國家梂準（CNS ) Α4規格（210X297公釐） 392092 ?I D8 六、申請專利範圍磺醢基氣亞胺基）_3，4一二甲氧基苄基氰化物，α_ (2 ，4，6-參（異丙基）——苯基一磺醢基氧亞胺基）-3，4 一二甲氧基苄基氰化物，α— (η—辛基磺醢基氧亞胺基）一 3，4一二甲氧基苄基氰化物，α_ (4——氛苯基磺醢基氧亞胺基）_3，4一二甲氧基苄基氟化物，α — (3—三氟甲基苯基磺酯基氧亞胺基）_3，4 —二甲氧基苄基氰化物， α -(甲基一磺醢基氧亞胺基）一4一甲基硫苄基氰化物， α— (4—十二烷基苯基磺醢基氧亞胺基）一 4 j甲基硫苄基氰化物，3— （4一甲基苯基磺醢基氧亞胺基）一 3，6 — 二甲氧基蒭，α - （4 —十二烷基苯基磺醯基氧亞胺基）一 3 ，6—二甲氣基葬，9一（ 4_甲基苯基磺醢基氧亞胺基 )一 1，6—二甲氧基薄，9一（ 4一十二烷基苯基磺睡基氧亞胺基）一 1，6 —二甲氧基荛，α_ (2，4，6—參（甲基 )苯基磺醢基氧亞胺基）一 3，4 —二甲氧基苄基氰化物， α - ( 4一硝基苯基磺醢基氧亞胺基）一3，4一二甲氧基苄基氰化物，(2 —丙基磺醯基氧亞胺基）一 4一甲基硫苄基氰化物，α — (4_氛苯基磺醢基氧亞胺基）一 4—甲經濟部中央標準局員工消費合作社印製 (請先閲讀背面之注意事項再Ϊ本頁) 基硫苄基氰化物，α — （3_三氟甲基苯基磺皤基氧-亞胺基）一 4一甲基硫苄基氰化物，α — (4—硝基苯基磺醢基一氧亞胺基）一 4—甲基硫苄基氰化物，α -(甲基磺醢基氧亞胺基）_3，4 —二硫甲基苄基氰化物，α_ (4 -甲基苯基磺醢基氧一亞胺基）一3，4—二硫甲基苄基氰化物， α — （4_甲基苯基磺睡基一氧亞胺基）一3—甲氧基一 4 — 本紙張尺度逍用中國國家揉準（CNS ) Α4規格（210Χ297公釐）經濟部中央揉牟局只工消费合作社印製 A8 B8 39209^_dI______ 六、申請專利範圍甲基硫一苄基氰化物，α_ (甲基磺醢基氧亞胺基）一3 — 甲氧基一 4一甲基硫一苄基氰化物，9一（η—辛基磺醱基氧亞胺基）一3，6—二甲氧基一蕹，9— (4 一十二烷基苯基磺醯基氧亞胺基）一 3，6 —二（4 一羥基乙基硫）—葬， 3 — （辑一 Μ基一 1— [4 —十二烧基苯基確睡基氧亞肢基〕一苄基）一 5，7—二丁氧基一番豆素。 12 .—種式I， la或lb的化合物，其於一光阻物霣中作為感光性酸提供者以供波長超過39 Q微毫米的鞴射。 Ϊ3. —種基於肟磺酸酯類之供波長超過390微毫米的輻射之光阻物質，該光阻物質包括一種式I，la或lb之化合物作為肟磺酸酷。 14. 根據申請專利範圍第13項的光阻物質，該光阻物質為一負性阻抗物質。 15. 根據申請專利範圍第13項的光阻物質，該光P且物質為一正性阻抗物質。 16. 根據申請專利範圔第13項的光阻物質，該光姐物質為一化學性擴大效果的咀抗物質。 -8 - 本紙張尺度逍用中國國家揉率（CNS ) A4规格（210X297公釐） (請先閲讀背面之注$項再ΐ本頁) 、11 A8 B8 392092_^_ 六、申請專利範圍 17 —種化學性擴大效果的正性姐抗物霣，其包括一種者供提酸性光感為作物合化之 b I 或 I I 式包其質物阻光性正的項 7^ 1X 第 ns a3 範利專請 ¢ 據根類物合聚的明透為仍時域區長波之米奄微 ο 8 1«* 達在括 (請先閲讀背面之注^^項再填寫本頁) I 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梂牟（CNS ) Α4規格（210X297公釐）1. A photoactivatable photoresist composition, comprising a) at least one compound, which can be cross-linked under the action of an acid and / or must be explicitly stated by the committee. Is the Kangshi changed after the amendment? Inside b) at least one compound whose solubility is changed by the action of an acid and c) at least one compound of the formula I as a light starter, whose weight of ingredients (a) and (b) is taken as 100 3: 1 to 15¾ weight, R; 0 II -C- -C = N-0-S0,-I 2 R, where a is 0 and X is 1; (Please read the precautions on the back page first) —f ml i · —— n ^ iiia ^ — ·-nf n! m · n ^ m · ml ^^ 1 In Order R, (I) Central Standard of the Ministry of Economic Affairs 扃 Monthly Industrial Cooperative Cooperative Printing Rt is phenyl, which is Or more than one radical is substituted, the radical may be Ci-Ctz alkyl, phenyl, OR 4 * SR4 and / or NR5R6, provided that when the benzene ring is substituted by a methoxy group, at least on the ring A further substituent group appears • or Ri is naphthyl, plaque or phenanthryl; radical Zeidyl, aryl and phenanthryl are unsubstituted or via Ci-C6 alkyl, phenyl, 0R4, SR4 and / or NRs IU This paper size is applicable to the Chinese National Kneading Rate (CNS) A4 specification (210x297 mm) A8 B8 C8 D8 6. Apply for a patent plus κ substitution; or a heteroaryl radical, which Is unsubstituted or substituted via Ci-Ce alkyl, OR4, SR4 and / or NRsR6M K, provided that Ri is not unsubstituted thienyl; ϋζ is unsubstituted or CN-substituted benzene Group, C2—Cs alkoxycarbonyl, CN; or Ri and R2 form a 5- or 6-membered ring, which is unsubstituted or substituted via Ct-Cs alkyl, OR4, SR4 or via NRslU plus M and One or more benzo radicals may be fused with it; it-, when X is 1, Ci—Cl 8 alkyl, Cl—C 4 alkyl or phenyl, radical phenyl may be unsubstituted or Substituted by one or more free radicals, which are halogen, Ci_C4 haloalkyl, CN, NO 2 * Ci-C t β alkyl, phenyl, OR 4; consumption by employees of the Central Bureau of the Ministry of Economic Affairs Cooperative printed bags (please read the precautions on the back and then this page) R4 is hydrogen, Ct-Ci z alkyl, which is unlithium substituted or 〇Η, substituted by K; Rs and Rs are each independently 氲 or "a Ci 2 alkyl group. 2. The photoresist composition according to the first patent application group, wherein in the compound of formula j, IU is phenyl The paper size is ^ 1% alkyl, 〇R4 -2- This paper size is applicable to China National Standards (CNS) Λ4 specification (210X297 mm) The Central Standards Bureau of the Ministry of Economic Affairs only prints A8 B8 C8 D8 6. Application Patent scope, S1U and / or replaced by NRs Rs plus K. 3. The photoresist composition according to item 1 of the scope of patent application, wherein in the compound of formula I, it is a heteroaryl radical which is unsubstituted or via Ct-Cs alkyl, 01U, SR4 and / Or single or multiple substitutions via NRS. 4. The photoresist composition according to item 1 of the scope of patent application, wherein in the compound of formula I, R2 is CN 05. The photoresist composition according to item 1 of the patent application, which is in the compound of formula I , R4 is (^-(6 alkyl), which is unsubstituted or substituted through a fluorenyl group. 6. The photoresist composition according to item 1 of the patent application scope, wherein in the compound of formula I, Rs Is "Ct a alkyl, Cr-(U haloalkyl, or phenyl, which is unsubstituted or via halogen, No 2, Ci-(4 haloalkyl, Ci-Cl 2 alkyl, R4 is substituted. 7. The photoresist composition according to item 1 of the scope of the patent application, wherein in the compound of formula I, b is 0 and is 1, and Ri is 3,4-dimethoxyphenyl, 3, 4-di (methylthio) phenyl, 3-methylamino- 4-methylthiophenyl or 4-methylfluorenyl, R2 is CN or 4-cyanophenyl, and R3 is phenyl- 3-This paper size is in accordance with Chinese National Standard (CNS) A4 (210X 297mm) (please read the "Cautions on the back side" before clicking this page) Order '^! Printing A8 B $ C8 D8 6. Scope of patent application, 4-monomethylphenyl, 4-methoxymethoxyphenyl, 3-trifluoromethylphenyl, 4-aminophenyl, methyl, isopropyl , Η-octyl, 2,4,6- (triisopropyl) -phenyl 4-mononitrophenyl, 2,4,6-trimethylphenyl or 4-dodecylphenyl, or Ri and R2 together form a manganese system, in which the aromatic ring is replaced by a methoxy or hydroxyethylthio plaque plus K. 8. The light nozzle composition according to item 1 of the patent application scope, further comprising component c) Μ In addition to further photo-starters, sensitizers and / or additives, the photo-starters are selected from the group consisting of self-starting photo-starters, these free-radical photo-starters are from diphenyl hydrazone Class, phenethylfluorene derivatives,? Dec —hydroxycycloalkylphenylfluorene, dialkoxyphenethyl, a — via radical one or a — limbyl phenethylhydrazone, 4 —arylene fluorenyl — 1, 3-dioxolanes, benzoin alkyl ethers and benzil aldehydes, or selected from monofluorenylphosphine oxides, diglycosylphosphine oxides, titanocenes, Halomethyltriazine derivatives, hexaarylbisoxazolyl compounds, cationic photoinitiators, peroxo compounds, aromatic sulfonium chrome or iodocarboxes, or cyclopentadienyl-arene-iron I) Mixed fluorenes. 9. The composition according to item 1 of the scope of patent application, which is used to prepare printing plates, color filters, impedance materials and image recording materials. 10. Compounds of formula lb -4- The size of this paper is applicable to the Chinese National Standard (CNS) A4 wash (210X297 mm) (Please read the note on the back before clicking this page) Order 39209¾ Application scope A8 B8 C8 D8 0 R, T: • C = N ~ 〇-SO ^ I 4R, • FU (lb) where Dl is 0 and X is 1; (Please read the precautions on the back before writing this page) Men's Workers Consumer Cooperatives, Central Procurement Bureau, Ministry of Economic Affairs Printed " is phenyl or naphthyl, which may be single or multiple substituted via Ci-Cs alkyl, phenyl, OR4, SR4 and / or NRS Re via radicals; or Ri 〃 is plaque or phenanthryl; Free radical and phenanthryl are unsubstituted or added via Cl-Cs alkyl, phenyl, OR4, SR4 and / or via HRs Re K --- or multiple mono-substitutions, provided that if "is benzene S substituted with OR4, at least one additional substituent SR4 or NRS Rs exists; or a heteroaryl radical, which is unsubstituted Or via Ci-C6 alkyl, OR4, SR4 and / or NRs Re plus K, provided that Ri 〃 is not an unsubstituted sulfanyl or furanyl; Rz is unsubstituted phenyl, C2 — Ce alkanoylcarbonyl, or CN; -5-This paper size uses the Chinese National Standard (CNS) A4 specification (210X297 mm) Order -¾ A8 B8 392092_ξ \ Application scope or ^ " and Rz formation A 5-or member ring, which is unsubstituted or substituted via Ci—Csfluorenyl OR4 ′ SR4 or via NRs Re plus K and one or more benzo radicals can be fused to it; R3, when X is 1 , Is Ct—CiS alkyl, Cl, C4 haloalkyl or phenyl, Czekiyl; free radical phenyl is unsubstituted or fluorinated by one or more halogens, Ci_C4 haloalkyl, CN, No2, C Branched-Ci s alkyl or 0 R 4 plus M substitution; 1 U is hydrogen, Ct-z alkyl, which is unsubstituted or substituted by 0 Η plus K; R 5 and Re Independent of each other is hydrogen or "-Ct 2 alkyl. Printed by the Central Government Bureau of the Ministry of Economic Affairs and Industrial Cooperatives Cooperative I (please read the precautions on the reverse side and then 本页 this page) 11. According to the compound in the scope of patent application No. 10, which is α_ (methylsulfonyloxyimine) Group)-3,4-dimethoxy-benzyl cyanide, α_ (4-dodecylphenylsulfonyloxyimino)-3,4-dimethoxybenzyl cyanide or α — (4-methylmethylphenylsulfonyloxyimino) — 4-monothiomethylbenzyl cyanide, α — (2-propylsulfonyloxyimino) — 3,4-dimethoxy Benzyl cyanide, 0 (-(phenylsulfonylaminoimino)-3,4-dimethoxybenzyl cyanide, α_ (4-methoxyphenyl-6-paper size 逋Using China National Standard (CNS) A4 specification (210X297 mm) 392092? I D8 6. Application scope of patents: sulfofluorenylimino) _3,4-dimethoxybenzyl cyanide, α_ (2, 4 ， 6-gins (isopropyl) —— phenylmonosulfonyloxyimino) -3,4-dimethoxybenzyl cyanide, α- (η-octylsulfonyloxyimino) ) A 3,4-dimethoxybenzyl cyanide, _ (4-phenylphenylsulfonyloxyimino) _3,4-dimethoxybenzyl fluoride, α-(3-trifluoromethylphenylsulfonyloxyimino) _3, 4-dimethoxybenzyl cyanide, α- (methylmonosulfonyloxyimino) -4-methylthiobenzyl cyanide, α- (4-dodecylphenylsulfonyl) Oxyimino group)-4 j methylthiobenzyl cyanide, 3- (4-methylphenylsulfonyloxyimino group)-3,6- dimethoxyfluorene, α-(4- 10 Dialkylphenylsulfonyloxyimino group) 3,6-dimethylamino, 9- (4-methylphenylsulfonyloxyimino group) -1,6-dimethoxy Thin, 9- (4-dodecylphenylsulfinoyloxyimino) -1,6-dimethoxyfluorenyl, α_ (2,4,6-p- (methyl) phenylsulfonyl) Oxyimino)-3,4-dimethoxybenzyl cyanide, α-(4-nitrophenylsulfonyloxyimino)-3,4-dimethoxybenzyl cyanide, (2-propylsulfonyloxyimino) -4-methylthiobenzyl cyanide, α- (4-aminophenylsulfonyloxyimino) -4-methyl Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Education (please read the precautions on the back before clicking this page) thiobenzyl cyanide, α — (3_trifluoromethylphenylsulfonyloxy-imino) 4-Methylthiobenzyl cyanide, α-(4-nitrophenylsulfonyloxyimino)-4-methylthiobenzyl cyanide, α-(methylsulfonyloxyimino) Amine) _3,4-Dithiomethylbenzyl cyanide, α_ (4-methylphenylsulfonyloxy-imino)-3,4-dithiomethylbenzyl cyanide, α — ( 4_Methylphenylsulfonyloxyimino) —3-methoxy-4—This paper is standard for China National Standards (CNS) A4 (210 × 297 mm). Printed by the Industrial and Consumer Cooperatives A8 B8 39209 ^ _dI ______ 6. Scope of patent application: methylthio-benzyl cyanide, α_ (methylsulfonyloxyimino)-3-methoxy-4-methylthio-benzyl Cyanocyanide, 9- (η-octylsulfonyloxyimino)-3,6-dimethoxy-amidine, 9- (4-dodecylphenylsulfonyloxyimino) 1 3, 6 — 2 4 -Hydroxyethylsulfur)-funeral, 3-(Edition 1M group-1-[4-dodecyl phenyl surelyloxyliminyl] -benzyl) -5,7-dibutoxy Ichibansu. 12. A compound of formula I, la or lb, which acts as a photosensitive acid provider in a photoresist for the emission of wavelengths in excess of 39 Q micrometers. Ϊ3. A photoresist based on oxime sulfonates for radiation with a wavelength of more than 390 micrometers. The photoresist includes a compound of formula I, la or lb as the oxime sulfonate. 14. According to the photoresist substance of the scope of application for patent No. 13, the photoresist substance is a negative resistance substance. 15. According to the photoresist substance of the scope of application for patent No. 13, the light P is a positive impedance substance. 16. According to the photoresist substance of the patent application No. 13, the photosensitizer substance is a chemically resistant substance that expands the effect. -8-This paper is scaled to the Chinese National Kneading Rate (CNS) A4 size (210X297 mm) (please read the note on the back before reading this page), 11 A8 B8 392092 _ ^ _ VI. Scope of Patent Application 17 — A positive chemical resistance compound with amplifying effect, which includes a type I or II for improving the acidity of photosynthesis of crops, including the positive light-blocking term of the substance 7 ^ 1X ns a3 Fan Lizhuan Please note that according to the transparency of the roots, it is still the long wave of rice in the time zone. 8 1 «* is included (please read the note ^^ on the back before filling this page) I order. --- „---- This paper is printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, and the paper size is applicable to China National Mou (CNS) Α4 specification (210X297 mm)