TW434455B - N-aryl-Α-amino acid of formula (I), photoinitiator compositions and photosensitive composition containing which, photosensitive material, and use of pattern formed by which - Google Patents

Abstract

A photoinitiator composition (A) comprising an N-aryl-Α-amino acid (I'), a 3-substituted coumarin (II) and an azabenzalcyclohexanone (III), or a photoinitiator composition (B) comprising an N-aryl-Α-amino acid (I'), a 3-substituted coumarin (II) and a titanocene (IV), or a photoinitiator composition (C) comprising a 3-substituted coumarin (II), a titanocene (IV) and an oxime ester (V), is effective for improving photosensitive properties of photosensitive materials containing poly(amic acid) and an addition polymerizable compound used for pattern formation.

Description

A7 434455 B7 V. Description of the invention (1) · The present invention relates to N-aryl-amino acids, using N-aryl-α-amino acids and 3-substituted coumarin and / or azabenzaldehyde Photoinitiator composition of cyclohexanone, using N-aryl_α-amino acid, 3-substituted coumarin and titanocene photoinitiator composition, using 3_ substituted coumarin , A photoinitiator composition of titanocene and oxime ester, using a photosensitive composition selected from the group consisting of these photoinitiator compositions, using a photosensitive composition selected from these photoinitiator compositions A photosensitive material of an element of the family and a method for forming a pattern using the photosensitive material. Photosensitive compositions are widely used to form cultural prints, relief images, photoresists, etc. (which typically use ultraviolet light (UV) as a light source) and are expected to have higher sensitivity . In particular, when photosensitive compositions are used for scanning by light exposure using a laser beam, they not only require high sensitivity, but also have sufficient sensitivity to visible light (4,58,488,5 14.5 nm). High sensitivity (this wavelength is the output wavelength of argon laser beam). In addition, in the case of photosensitive polyimide that can be used for thick films in semiconductors, a g-line stepper (using monochromatic light (4 3 5 nm light)), a contact exposure device (using a mercury lamp) (All wavelengths), and specular projection exposure equipment has sufficient sensitivity, and has excellent photosensitivity wavelength properties. To enhance sensitivity, various investigations have been conducted on photoinitiators. As for the lightening agent, benzoine and its derivatives, substituted or unsubstituted polynuclear M, and the like are known. However, materials with excellent sensitivity that meet the above criteria have not been known so far. On the other hand, the polyimide or its precursors with photo-patterned properties are suitable for the paper size of China National Standards (CNS) 64 (210 × 297 mm) __ ^ -------- clothing ------ 1Τ ------ ^ (Please read the notes on the back before filling out this page) Printed by the Male Sample Consumer Cooperative of the Central Sample Bureau of the Ministry of Economic Affairs 4 34 4 5 5 B7 Central Ministry of Economic Affairs 搮Standard Bureau 1GE; Printed by Industrial and Consumer Cooperatives 5. Invention Description (2) 1 The body is called% photosensitive polyimide •, which is discarded as a semiconductor. Table 1 I Protective film 0 In order to give polyimide Photosensitivity 9 There are many known methods. 0 I 1 For example 9 Japanese Patent Unexamined Publication (JP — B) · * | | Please 1 1 5 5 — 4 1 4 2 No. 2 discloses the use of hydroxyacrylate Poly (first M \ read 1 amino acid) method. Japanese Patent Unexamined Bulletins are backed. I 5 7 — 1 7 0 9 2 9 and 5 4 -1 4 5 7 9 4 reveal that by mixing t-1 poly (amidoamine) and amino acrylate, Introduce photosensitivity using salt bonding and then 1 1 sex group 0 in front-case (JP —B) The photo-patterning property is to fill in this 1 | quite good 9 but because it is difficult to obtain high polymer, photo-sensitivity The removal of the base 1 I group becomes quite incomplete, resulting in the disadvantage of poor film properties. The other 1 I — aspect, in the latter case (two J p —A cases), it is easy to obtain lettuce polymer and excellent film properties because of the volatility of 1 1 1, but the photocathode 1 is finalized The nature is insufficient. Especially in the case of a thick film 1 1 having a film thickness of 5 μm or more, a photosensitized polyimide is used, and when exposed to light after curing (use 1 | use 1 — thread Stop (3 6 5 r 1 m light) ig " -line Sepper (1 1 4 3 5 η m light)) specular projection type exposure equipment (using a mercury lamp \ all wavelengths) without any good patterning Questions about properties 0 1 1 1 Summary of the invention • 1 1 | The object of the present invention is to provide a photosensitive composition 1 having excellent photosensitivity and a photoinitiator composition for a photosensitive material. 1 A method for forming a pattern using a photosensitive material (that is, N-aryl-α-amine 1-based acid as a photoinitiator) 9 A method using N-aryl-a II-amino acid and 3- Substitute coumarin and / or heterobenzaldehyde cyclohexanone 1 1 1 The size of this paper is applicable to Chinese national standard (CNS 丨 A4 Specification U 丨 ο X 297) )

-4 34455 A7 B7 V. Explanation of the invention (3) · Photoinitiator composition using N-aryl-β-amino acid and 3 _ substituted coumarin and / or azabenzaldehyde cyclohexanone Light starter composition using N-aryl-π-amino acid, 3-substituted coumarin and titanocene light starter composition using 3-substituted coumarin, dicene A photoinitiator composition of titanium and oxime vinegar, a photosensitive material using one element selected from the family of these photoinitiator compositions, and a pattern forming method using the aforementioned photosensitive material to overcome the above-mentioned prior art problems. According to the novel composition of the present invention, the above-mentioned non-excellent patterning properties cannot obtain the above-mentioned excellent patterning properties when exposed to i-line stepper, g-line stepper, and mirror projection type exposure equipment (using all wavelengths of a mercury lamp). Problems can be solved. The present invention provides N-aryl_α_amino acid q5 7'7 in the formula:

Rl, I? 2, R3, R4 and Rs respectively represent a gas atom, a tooth atom, (Ci-4) alkyl, cyano, (C2-1〇) alkoxycarbonyl, formamidine, or (Ci-4 ) Alkanesulfonyl, and the aforementioned alkyl moiety may be substituted with an alkyl group, and at least one of R:-R5 is an alkoxy group or (Ci-4) alkanesulfonyl, Re is not a gas atom, (Cl-12 ) Academy, Ring Academy "(Cl-12) Hydroxyalkyl, (C2-12) Alkoxyalkyl, (Cuz) Aminoalkyl This paper is applicable to national standards (CNS) A4 (210X297) Mm) | _ ^ 丨, ^ .—, --- 袈 ------ Order ------ 姝 (Please read the notes on the back * before filling out this page) Central Bureau of Standards, Ministry of Economic Affairs Printed by the Shellfish Consumer Cooperative «Instructions of the Shellfish Consumer Cooperative by the Central Bureau of quasi-Ministry of Economic Affairs 4 34 45 5 A7 ~ B7 V. Description of the invention (4) ', or aryl group: and R8 each show a hydrogen atom or (Ci -8) Alkan i 0 The present invention also provides a photosensitive composition (A), which comprises: N-aryl-a-amino acid represented by the general formula (I-), and at least one element selected from the following:

In the formula:

Rs, Rio, Rll, and R13 each 7TC gas atom, amine group substituted with (Ci-5) alkyl group, amine group substituted with two (Ci-5) alkyl group, (Cn) alkoxy group, 醯Oxy, aryl, halogen, or (Ci-5) sulfanyl; and R14 represents an unsubstituted phenyl, biphenyl, ortho, phenyl, benzofuryl, furyl, pyridyl Coumarin group, amine group, amine group substituted with 1 or more (Ci-5) alkyl group, cyano group, () alkoxy group, (Cl-5) alkyl group, halogen atom, haloalkyl group, Formamyl, (Ci-5) alkoxycarbonyl, (Cn) oxy, via (

Ci-s) fluorenyl, alkyl, alkoxy or (Cn) fluorenyl-substituted phenyl, the aforementioned biphenyl, a certain group, fluorenyl, benzofuranyl, furanyl, pyridyl, or coumarin The prime group can be substituted with (Ci-5) fluorenyloxy or (Cn) fluorenyl, and azabenzaldehyde cyclohexanone represented by the following formula: The paper scale is applicable to the Chinese National Standard (CNS) A4 (210X297) (Mm) 1 ^ |, ^ (please read the note on the back before filling in this page) w 4 3 4 4 5 5 4 34 40 〇A7 B7 V. Description of the invention ('2 3

20 25 23 (III) where R 1 5 represents hydrogen C 1 -C 1- C 7 -ylcarbonyl. The following general formula: R16 'Rl7' RlS, Rl9, Rz0 * R21 and R22 each atom, chlorine atom, bromine atom, (Ci-u) alkyl, aryl or (12) alkoxy group: and R23 , R24, R25, and R26 each represent a (6) alkyl group; X represents an imino group, which may be via a (Ci-U) alkyl group, (2.) an arylene group, 5 aryl group, (C2-2I) acid group > (C7-20) aryl, (C2-I2) hydrazone or 'Ct-2.'

The present invention also provides a photoinitiator composition (B which includes N-aryl-amino acid represented by (I >), 3-substituted coumarin compound represented by (II); and Titanocene: 1 ^ 丨.! —.---- 袈 ------ Order ------ Line (Please read the notes on the back before filling this page) Ministry of Economic Affairs Yindong, the Consumers Cooperative of the China Standards Bureau

In the formula, each of R (IV) and R36 shows a hydrogen atom, _ atom, (Ci-2.) Alkali paper size General Chinese National Standard (CNS) A4 specification (210X297 mm) 4 34455 A7 B7 V. Description of the invention ( 6) An oxy group or a heterocyclic ring (e.g., 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, imidazolyl, pyrazolyl, etc.), the aforementioned heterocyclic ring is bonded to a benzene ring via an alkylene group Or substituted with one or more alkyl, amino and alkoxy groups. The present invention also provides a photoinitiator composition (C), comprising: a 3-substituted coumarin represented by the general formula (II), a titanocene compound represented by the general formula (IV), and Shown oxime ester: 0 〇

〇 In the formula: R37 and 1 ^ 38 are each a gas atom * (Cl-6) fluorenyl group, (Cl-6) oxygen or nitro group; and R39 is not (Cl-12) disease group, (Cl-12 ) Methoxy, phenyl, benzyl, —OCH2CH2OCH3 or —C02CH2CH3 ° The present invention also provides a photosensitive composition comprising: at 1 atmospheric pressure, a boiling point of i 0 o ° c or higher Addition polymeric compounds, and photoinitiator compositions (A), (B) or (C). The present invention also provides a photosensitive material, which comprises: (a) poly (amidic acid), (b) carbon with one or more dimerization or polymerization using actinic rays-this paper窣 (CNS) Α4 Specification (2! 0X297 mm) — -ΤΙΓΤΙΤ-, --- ^ ------ Order ------ (Please read the precautions on the back before filling this page) Printed by the China National Quasi-Statistical Bureau of the Ministry of Qing Dynasty, 4 34 45 5 A 7 B7 V. Description of the invention (7) 'Carbon double bond and one or more amine groups or their quaternary salts: and ( c) Photoinitiator composition (A), (B) or (C). The present invention also provides a detailed description of the method Q for forming a pattern using the photosensitive material described above. The N-aryl-α-amino acid system of the present invention is represented by the following general formula: R1 Rs ^

---p Jl · ^^^^ 1 _ (Please read the notes on the back before filling out this page) In the printed format of the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs: R 1, R2, R3, R4 and Rs respectively Showing a hydrogen atom, a halogen atom, a (C: -4) alkyl group, an oxy group, a (C2-1〇) alkoxycarbonyl group, a methylamino group, or a (Ci-4) alkylsulfonyl group, and the aforementioned alkyl portion May be substituted by chloro, and at least one of Ri-R5 is cyano or (Cn) alkylsulfonyl: R6 毎 (atom, (Cl-12) alkyl, cycloalkyl, and (Cl-12) hydroxyl Alkyl, (C2-12) alkoxyalkyl, (Ci-12) aminoalkyl, or aryl; and R7 and R8 each represent a hydrogen atom or (Cn) alkyl. When using the general formula (I ) When the compound is in the photoinitiator composition, * and at least one rule __R5 is a cyano group or (Ci-4) alkylsulfonyl group, and the restriction is unnecessary [hereinafter, this compound is called N—Aryl-α-Amino Acid # of 'General Formula (I-)]. This paper size is applicable to China National Kneading Car (CNS) A4C grid (210 ×: 297 mm) _' 10-Line 4 34455 A7 B7 Consumption cooperation among employees of the Central Bureau of Procurement, Ministry of Economic Affairs (8) * 1 1 N-aryl—a monoamino acid 1 1 represented by the general formula (I) or (I) can be used, for example, for class I 1 for ntg substituted halobenzene and glycine compounds A similar method of aromatic nucleophilic substitution reaction is made into more detailed and g- aromatic nucleophilic substitution reaction usually can be made by substituted halo group first W 1 I benzene and glycine compounds (about equal mole number) 9 in Polar aprotic solvents read back 1 | (such as diketone y dimethyl acetal, N — methyl — pyrrolidine m NB Note 1 meaning N — * methyl acetamide Ν Ν>> Ν — dimethyl methyl Ammonium tetrahydrofuran f Matter 1 I and 1 1 m 焼 (SU 1 f 〇1 an e), methyl ethyl ketone 9 ethylene carbonate 9 etc.) Among the f is in the presence of a fluorene compound at room temperature to about 1 0 0 ° C 0 to 1 Page 1 I for basic compounds 9 Sodium carbonate can be used * Etc. 0 1 | Examples of compounds of general formula (I) or (I-) are 1 1 N-(p-methylsulfonylphenyl)-Ν-methylglycine (compound 1 1 order 1) N (P-monomethylsulfonylphenyl) — Ν —ethylglycine fluorene 1 1 | N — (p-methylsulfonyl phenyl) — Ν mono-n-butylglycine 1 1 N — (p- (Gasylphenyl) — Glycine (Composition • i.-) 1 N — (p-cyanomethylsulfonylphenyl) 1 N — methylglycine 1 IN — (p-cyanide Methylmethanesulfonylphenyl) — N —ethylglycine, • 1 1 N — (p-cyanomethylsulfonylphenyl) — N —n-propylglycinate 1 N (p-amino Methanesulfonylphenyl) — N —n-butylglycine 9 1 1 N — (p-Ethylsulfonylphenyl) — Ν —Methylglycine > 1 IN — (P-ethanesulfonyl Phenyl) — Ν —ethylglycine SIN — (p-ethylsulfonyl Group) — Ν —n-propylglycinate 1 1 N — (p-ethanesulfonylphenyl) 1N-n-butylglycine 1 1 1 > A4 specifications (210X297 mm) Indian policy of the Central Laboratories of the Ministry of Economic Affairs, Pak Gong Consumer Cooperatives, 4 34 4 5 5 A7 B7 V. Description of the invention (9) 'N— (yield 2 / -Gasylsulfonium Phenyl) _N-methylglycinic acid 9 Λ Ν— (p--2 * cyanoethanesulfonylphenyl) -N-ethylglycine N— (p-2-2cyanoethanesulfonyl) Phenyl) -N-n-propylglycine, N- (p-2-aminoethanesulfonylphenyl) -N-n-butylglycine, N- (p-m-phenyl) -N —Methylglycine (compound 3), N— (p-glycylphenyl) —N—ethylglycine, N— (p-cyanophenyl) —N—n-propylglycine, N — (P-monophenyl) —N —n-butylglycine, N— (p-n-propylsulfonylphenyl) —N —methylglycine, N — (p-n-butylsulfonyl) Phenyl) -N-methylglycine, N- (p-carboxamidophenyl) -N Methylglycine, N- (p-carboxamidophenyl) -N-ethylglycine, N- (p-carboxamidophenyl) -N-n-propylglycine, N -(P-Carboxamidophenyl) -N-n-butylglycine, N- (p-ethoxycarbonylphenyl) -N-methylglycine, N- (p-ethoxyoxy Phenyl) -N-ethylglycine, N- (p-ethoxycarbonylphenyl) -N-n-propylglycine, N- (p-ethoxycarbonylphenyl) -N-n-butyl Glycine, N- (p-methoxycarbonylphenyl) -N-methylglycine, N- (p-methoxycarbonylphenyl) -N-ethylglycine, This paper is suitable for China® Furniture standard (CNS) A4 size (210X297 male) ~~ '-彳 ---- Ί, --- Qi 1 ------ order ----- (Please read the note on the back first Please fill in this page again for matters) -12-， r 4 34 4 5 5 A7 B7 Imprint of the 8th Industrial Cooperative Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (10)-1 1 N — (p-methoxycarbonylphenyl) ) -N-n-propylglycine 1 1 N-(p-methoxycarbonylphenyl)-N -n-butylglycine Acids, etc. 〇1 1 These compounds can be used alone or in the form of a mixture (when used as a light initiator _-| 1 agent) for use 0 Please read _ | 1 These compounds are effective as a light initiator > It uses UV and visible read back Sj 1 II light and combines 1 or more appropriate photosensitizers to generate active groups 0 winter 1 P [Photoinitiator composition (A) of the present invention contains _ item 1 I again 1 1 The above general formula (I) shows N — aryl — a monoamino acid 9 to fill in this and at least selected from the following: " — element 0 page 1 I shown by the following general formula 3 — substituted coumarin Compound 1 1 I ^ 1 3 〇1 1 | ^ 1 Q 1, R 14 1 (II) 1 «11 γ, 〇, 〇1 R12 1 I in the formula 4 1 1 t R > R 1 0 »R 1 1 > R 12 and R 13 each show a hydrogen atom replaced by an amine group of (i.e. C 1-S) fluorenyl skirt, and substituted by two (C! -5) alkyl groups. 1 Amine > (C 1-5) fluorenyl, fluorenyl, aryl (such as phenyl 9 I 1 a certain group, etc.) Ϊ halogen atom, or (C 1-5) thiol: and R 1 4 shows unsubstituted phenyl, biphenyl, lyl 9 m aryl, benzofuranyl, 9 furanyl, 1 furanyl, pyridyl, coumarinyl J amino, 1 or more (C 1-5) 1 1 1 Alkyl substituted amine, cyano (C 1-5) fluorenyl (C 1-5) i fluorenyl, halogen atom, halofluorenyl > formamyl > (C 1-5) oxocarbonyl group]] 1 (C 1-5) fluorenyl group * via (C 1-5) oxo group 9 cyano group, oxo group 1 1 1 CNS) 6.4 specifications (210X297 mm) -13-4 34 4 5 5 A7 B7 5. Description of the invention (11) 'or (Ci-s) fluorenyl-substituted phenyl, the aforementioned biphenyl, fluorenyl, Umyl An aryl, furfuryl, pyridyl or coumarin group may be substituted with (Ci-s) fluorenyl or (Cps) fluorenyl, and a titanocene compound represented by the following formula: 1 Ξ3

2G 2 5 (III) In the printed format of the Men ’s Workers ’Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs: Rl55 Rl6» Rl7 > Rl8 * Rl9 (Such as phenyl, a certain group, etc.) or (C12) alkane: and R23, R 2 4 'R 2 5 and R 2 6 each (C 1-6) alkynyl group; X shows imino group , Which can be via (Cl-lZ) alkyl '(C7-20) aralkyl (such as benzyl, phenethyl, etc.), aryl (such as phenyl, fluorenyl, etc.), (* C2-21) Alkyl '(C7-20) arylfluorenyl, (c2-12) oxoyl, or (C 7-2.) Aryloxycarbonyl substituted. 'General formula (Π) 3 ~ Substituted coumarin compounds For example, 3-phenylfluorenylcoumarin, 3-phenylfluorenyl_ 7-methoxycoumarin, 3-phenylfluorenyl_ 5,7-dimethoxycoumarin, 3_ (4 > -fluorophenylphenylfluorenyl) -coumarin, 3- (4--fluorenylphenylfluorenyl) -7-methoxycoumarin ,

RR 21 and R 22 each ^ H binding. 1 thread,. (Please read the precautions on the back before filling out this page) This paper is a universal standard for solid state countries (CNS) A4 wash (210 X 297 mm) ) 14 4 34 4 5 5 A7 B7 Printed by the Anti-Poverty Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Invention Description (12) 4 i 1 3 — (4 1 —Cyanophenylhydrazone) — 5, 7 — Dimethoxy Base coumarin 1 1 3 —sleep carbonyl coumarin 9 1 1 7 — methyl — 3 — thienylcarbonyl monocoumarin 9 _ |! Please 1 \ 5 9 7 — dimethoxy — 3 Iridylcarbonyl — coumarin, read first. 1 I 7 _ diethylamino — 3 —thienylcarbonyl — coumarin J Read back 1 »1 side 1 7 — dimethylamino — 3 — blind Note of umylcarbonyl-coumarin 3-(4 a-methoxyphenyl fluorenyl) coumarin Ϊ matter 1 I again 1 1 3 one (4--a Oxybenzyl)-7-methoxycoumarin, fill out this 3 (4 〆methoxyphenylbenzyl) 5 > 7 dimethoxycoumarin page 1 1 I 3 5 3 one-carbonyl Bis- (7-diethylaminocoumarin), 1 1 f 3, 3 1-carbonylbis- (7-methoxycoumarin) 9! Order 3, 3-mono-carbonylbis- (5, 7 — Dimethoxycoumarin), etc. 0 1 1 These compounds can be used alone — or in the form of mixtures. 0 t 1 Examples of azabenzaldehyde cyclohexyl 31 shown in Example (III) are as follows. Second line I 2 > 6-bis (p-N > Ν-diethylaminobenzaldehyde)-4--methyl 1 t-4 monocyclohexanone 1] 2 6 -bis (p-N 5 Ν-di Methylaminobenzaldehyde) — 4--methyl-1 — 4 monocyclohexanone 1: | 2, 6-bis (p-—N—N—diethylaminobenzaldehyde) — 4—-methyl1 ί 4 Hexanehexanone • > 1 2 6-Bi (p-N Ν-dimethylaminobenzaldehyde) — 4--ethyl 1 1 — 4 —M Hexanehexanone »1 I t Paper scale Applicable to China National Standard (CNS) A4 specification (210 > < 297 males > -15 " 4 3 4 ^ 5 5 A7 B7

Ministry of Economy _ Printed by the Sample Cooperating Bureau Shellfish Consumer Cooperative Co., Ltd. 5. Description of the Invention (l3) 2, 6-Bis (p-N,, N--diethylaminobenzaldehyde)--4 -n-propyl a 4 ~ M heterocyclohexanone; 1 2, 6 -bis (p-N: 丨 N--dimethylaminobenzaldehyde)--4-n-propyl 4-~ aziridanone; > t 2, 6--bis (p-N '丨 N-diethylaminobenzaldehyde)--4--phenethyl-4-~ Μ heterocyclohexanone; 1 1 2, 6--bis (p- Ν, 'N-_ monomethylaminobenzaldehyde)--4--benzyl-4--want heterocyclic hexanone: 2, 6--bis (welcome «p-Ν, N--dimethylamine Benzaldehyde)--4--acetamidino-4-~ Μ heterocyclohexane m; 2, 6--bis (p-N, N-_. Methylaminobenzaldehyde)--4 ~ -phenylhydrazone Radicals 4 to 6 heterocyclohexane; etc. These compounds can be synthesized by the method disclosed in U.S. Patent No. 4,988,507. These compounds may be used singly or as a mixture thereof. N —aryl monoamino acid represented by general formula (I <) and 3-substituted coumarin compound represented by general formula (II) and / or azabenzaldehyde cyclohexanone represented by general formula (II) The compounds can be used in various ratios, but the N-aryl-α-amino acid represented by the general formula (I-) is preferably used in a larger amount than the compounds of the general formula (II) and / or (III). In general, when a compound of the general formula (II) or (III) is used, the number of the compounds of the general formula (II) or (III) is set to 1 to 100 parts by weight and 100 parts by weight. Compounds of general formula (I /), and in the case of using compounds of general formulae (II) and (III), the total number of compounds of general formulae (Π) and (III) is 1 CNS A4 Grid (210X297mm) — ----------------------- Order (please read the precautions on the back before filling in this page) -16-4 34 45 5 A7 B7__ 5. Description of the invention (14) · 100 parts by weight / 1 100 parts by weight of the compound of the general formula (I <). Another photoinitiator composition (B) of the present invention comprises: N-aryl-α-amino acid represented by the general formula < I >), and 3-substituted fragrant compound represented by the general formula (II /) Beans, and titanocene compounds of the formula:

In the formula: R27 to R28 each represent a hydrogen atom, a halogen atom, a (Cuo) alkoxy group or a heterocyclic ring (such as pyrrole, etc.), and the aforementioned heterocyclic ring is bonded to a benzene ring via an alkylene group or via 1 or more Alkyl, amine and alkoxy substituted. Examples of the titanocene compound represented by the general formula (IV) are as follows: bis (cyclopentadienyl) _bis [2,6-difluoroyl-3 — {2-(1 H-pyrrole-1 _yl) Ethyl} phenyl] titanium: bis (cyclopentadienyl) -bis [2,6-difluoroyl-3_ {2- (1H-pyrrole-1-yl) propyl 丨 phenyl] titanium; bis ( Cyclopentadienyl) a bis [2,6-difluoroyl-3— {2- (1H-pyrrole-I-yl) methyl} phenyl] titanium: bis (cyclopentadienyl) a bis [ 2,6—difluoro-3— (pyrrole-1 1-yl) phenyl] titanium; the paper's standard is applicable to China National Standard (CNS) A4 (210X: 297 *) H 1J--II. ··· , — II— i--....... Ding_ I — ^ 1 1-- _ I '-I > \ W3 i Shun (Read the precautions on the back and then fill in the purchase) Economy Ministry of Work, Central Government, Associated Bureau, Consumers and Consumers Cooperatives -17-434455 A 7-B7__ 5. Description of the invention (15) 'Double (cyclopentadienyl) ~ double [2,6 —two gas base — 3 — ( 2 '5 -dimethylpyrrole-1-yl) phenyl] titanium; bis (cyclopentadienyl) -bis [2,6-difluoroyl_3- (2,5-diethylhexyl) _ 1-yl) phenyl] energy; bis (cyclopentadienyl) -bis [2 »6-dioxo-3— (2, 5-diisopropylpyrrole-1 mono) phenyl] titanium ; Bis (cyclopentadienyl) -bis [2,6-difluoroyl_3_ (2,5-bis (dimethylamino) pyrrole-1-yl) phenyl] titanium; bis (cyclopentadiene Group) —bis [2,6-difluoro-3— (2,5-dimethyl-1,3-methoxypyrrole-1, 1-yl) phenyl] titanium: bis (cyclopentadienyl), a double [2,6-difluoroyl-3-methoxyphenyl] titanium; bis (cyclopentadienyl) -bis [2,6-difluoroyl-3-ethoxyphenyl] imine; bis ( Cyclopentadienyl) —bis [2,6-difluoroyl-3-isopropoxyphenyl] titanium; bis (cyclopentadienyl) —bis [2,6-difluoroyl-3—n Propoxyphenyl] titanium; etc. These compounds may be used singly or as a mixture thereof. The compound of the general formula (II) and the compound of the general formula ([V) can be used in various kinds of BJ, but the number of the compound of the general formula (II) is preferably 1 to 100 parts by weight, and the compound of the general formula (IV) The amount used should be 10-30 parts by weight (relative to 1 (30 parts by weight of the compound of the general formula (I /). The paper scale is applicable to the Chinese national rubbing (CNS) A4 washing Grid (210X297 mm) 丨 ^^ [ΜΙΡΟ --- 'installation --- order ------. Line (please read the notes on the back first and fill in this f) Central Ministry of Economic Affairs Negative work consumer cooperatives India Printing and Finance Ministry of Economics Central Standards Bureau Employees Consumer Cooperatives India Cooperative 4 34 45 5 A7 B7 Five 'Invention (16)' Another photoinitiator composition (C) of the present invention contains: (II) 3—Substituted coumarin compounds, titanocene compounds represented by general formula (IV): and oxime ester compounds represented by the following formula:

0 0 R

Θ 3 R

In the formula, R37 and R38 each represent a nitrogen atom, (Cn) alkyl, (Ci-e) alkyloxy or nitro group; and R39 is not (Ci-i2) alkyl, (Ci-u) alkoxy Examples of phenyl, benzyl, -〇CH2CH2〇CH3 or -CO2CH2CH3 ° compounds of general formula (V) are as follows:

— Ί — ---- k .------ Order ------ Line {Please read the precautions on the back before filling this page) This paper is a standard for China Standards (CNS) A4 Specifications (210X297 mm) -19-

ο 〇 Ο 4 34 4 5 5 A7 B7 V. Description of the invention (〗 7) · Ο ο 0 0

These compounds may be used singly or as a mixture thereof. The compounds of the general formulae (II), (IV) and (V) can be used in various proportions, but it is preferred that the amount of the titanocene compound and the oxime ester compound is more than 3-substituted coumarin. More specifically, the amount of the compound of the general formula (II) is preferably 1 to 100 parts by weight, and the amount of the compound of the general formula (IV) is preferably 10 to 3 0 parts by weight (per 100 parts by weight). Parts of general formula). The photosensitive composition of the present invention comprises: an addition polymerizable compound having a boiling point of 1000 ° C or higher at 1 atmosphere, and a photoinitiator composition (A), (B) or (c). The photosensitive composition also contains (if necessary) one or more conventional photopolymerization initiators. Examples of photopolymerization initiators are as follows: Michler ketone: benzoin methyl ether: benzoin ethyl ether: benzoin isopropyl ether: 2-third butyl ketone; This paper size is applicable to China National Standards (CNS) A4 * MS · (210 × 297 mm) --TMI.JI --- k, ------ order ------ line (please read the back first) Note for refilling the lettuce page) The Central Labor Bureau of the Ministry of Economic Affairs prints the monthly labor cooperative of the Ministry of Economic Affairs and the Central Standards Bureau of the Ministry of Economic Affairs prints the production of shellfish consumer cooperation Du 34 4 4 5 5 A 7 _B7_ V. Description of the invention (18) 2 —Ethylfluorenone; 4, 4 ** —Bis (N, N_diethylamino) benzophenone: Acetophenone: Acetophenone; thioxanthone; 2, Dimethoxy-2_ Phenylphenethyl copper: 1-hydroxycyclohexylphenyl ketone: 2-methyl- [4- (methylthio) phenyl]-2-morpholine-1 1-acetone, benzyl alcohol (benz i): Diphenyl disulfide; phenan threnequ i none; 2-isopropyl blind tonone; rebuffrafen tetrabutyrate; N-phenyldiethanolamine; 2- (0-ethyl Oxycarbonyl) oxyimino — 1,3-diphenyl-propane Alkanedione: 1-phenyl-1 2- (0-ethoxycarbonyl) oxoximepropan-1-one; 3,3-, 4,4 tetrakis (third butylperoxycarbonyl) benzophenone; etc. These photopolymerization initiators can be used singly or in the form of a mixture thereof. The photopolymerization initiators can be used in various proportions. The addition polymerizable compound must have a boiling point of 100 ° C or higher (at 1 atmospheric pressure). Bottom). When the boiling point of the addition-polymerizable compound (the Chinese National Standards (CNS) Standard 4 < Grid (210X297 mm) is applied at the scale of this paper) ------; --- ---- --- 1T ------ 0 1-(Please read the precautions on the back before filling this page) -21-

5L 434455 A7 B7 printed by the Central Bureau of Standards and Quarantine of the Ministry of Economic Affairs. 5. Description of the invention (19) 1 At atmospheric pressure, the solvent in the system is removed when it is lower than 100 ° C. (For example, drying ) Or evaporate when irradiated with actinic rays, resulting in unsuitable properties. In addition, in order to obtain a homogeneous composition containing a photoinitiator composition, it is preferable to use one which is soluble in an organic solvent which is convenient to use. As the solvent for the photosensitive composition, acetone, methyl ethyl ketone, diethyl ketone, toluene, chloroform, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2 -Butanol, tertiary methyl ethyl ketone, ethylene glycol

Monomethyl ether, ethylene glycol monoethyl ether, xylene, tetrahydrofuran, dioxane, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, r — butyrolactone, dimethylasyl, ethyl carbonate, propyl carbonate, sulfane, etc. These solvents may be used singly or as a mixture thereof. As for the addition polymerizable compound having a boiling point of 100 ° C or higher at 1 atmospheric pressure, it is preferable to use one obtained by the condensation reaction of a polyhydric alcohol with π, a point-unsaturated carboxylic acid. Examples of the aforementioned compounds are as follows: di (meth> ethylene glycol acrylate (di (meth) acrylate means, diacrylate # or, dimethacrylate ^, all of which are described below in this way), Triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, di (meth) acrylate 1,2 — Propylene glycol ester, bis (meth) acrylic acid di (1,2-propylene glycol ester), this paper size is applicable to China National Sample Rate (CNS) A4 grid (210XW7 male) J .---:-^ --- 'Loading ------ ordering -----, please read the notes on the back before filling this page) -22-4 34455 A 7 B7 V. Description of the invention (20) · Di (methyl ) Tris (1,2-propylene glycol) acrylate, tetra (1,2-propylene glycol) di (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate Esters, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, 1,4-monobutylene di (meth) acrylate Mono-1,6-butanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, styrene, divinylbenzene, 4-vinyltoluene, 4 —Vinylpyridine, N —vinylpyrrolidone, 2-hydroxyethyl (meth) acrylic acid, 1,3- (meth) propenyloxy-2-hydroxypropane, methacrylamine, N, N-dimethylacrylamide, N-methylmethacrylamine, etc. These compounds may be used singly or as a mixture thereof. The photoinitiator composition (A), (B) or (C) is used in an amount of 0.01 to 30% by weight, preferably 0.05 to 10% by weight (in terms of photosensitivity and film strength, The boiling point is 100 ° C or higher (in this paper standard, the national standard (CNS) A4 wash grid (210 × 297 mm): 丨 J--1. Ί ^ ------ order-- ----- Μ (Please read the notes on the back before filling out this page) Printed by the Central Government Standards Bureau, Ministry of Economic Affairs, Only Consumer Cooperatives-23-A7 4 34 45 5 B7 V. Description of the Invention (21) ^ 1 atmosphere Force) based on the weight of the addition polymerizable compound). The photosensitive composition of the present invention may further include (if necessary) 1 or more organic polymers having a molecular weight of 100 to 70000. Examples of organic polymers are as follows: (A) Copolyesters are composed of polyhydric alcohols (eg, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, neopentyl glycol, etc.) and polyvalent Copolyesters prepared by the reaction of carboxylic acids (e.g., p-acid, isophthalic acid, sebacic acid, adipic acid, etc.). (B) vinyl polymer vinyl monomer (such as methacrylic acid, acrylic acid, methacrylic acid, or alkyl acrylate, for example, methyl (meth) acrylate, ethyl (meth) acrylate, ) Butyl acrylate, 2-hydroxyethyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate , (Meth) acrylic acid 2-ethylhexyl, etc.). (C) Polyoxymethylene (D) Polyurethane (E) Polycarbonate (F) Polyamidamine (G) Poly (amidate) Poly (amidate) Polytetracarboxylic dianhydride and diamine Made by addition polymerization of compounds. Examples of tetracarboxylic dianhydride are as follows: Pyromellitic dianhydride, this paper is in accordance with the Chinese National Standard (CNS > A4 size (210X 297)) IJ ^ II II Order 1 Spicy (Please read the precautions on the back first) (Fill in this page again) Printed by the Central Laboratories Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives 24-Printed by the Central Government Bureau of the Ministry of Economic Affairs, Consumers 'Cooperatives ^ 4 34455 A7 B7 V. Description of Invention (22)' 3, 3 >, 4, 4 ^ —benzophenonetetracarboxylic dianhydride, 3,3 —, 4,4 > —biphenyltetracarboxylic dianhydride, 1,2,5,6 —a certain tetracarboxylic dianhydride, 2,3,6 , 7-fluorenetetracarboxylic dianhydride, 2,3,5,6_pyridinetetracarboxylic dianhydride, 1,4,5,8 —A tetracarboxylic dianhydride, 3,4,9,1 0- Perylene tetracarboxylic dianhydride, 4,4-monosulfofluorenediphthalic dianhydride, m-bitriphenyl-1,3,3,4,4,4-tetracarboxylic dianhydride, Bistriphenyl-3,3,4,4,4-tetracarboxylic dianhydride, 4,4-mono-oxydiphthalic dianhydride, 1,1'1'3,3,3_hexakisyl-2, 2 —bis (2,3 dicarboxyphenyl) propane dianhydride, 1,1,1,3,3,3 Hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 1,1,1,3,3,3 -hexafluoro-2,2-bis [4 one (2, 3_dicarboxyphenoxy) phenyl] propane dianhydride, 1'1'1'3, 3,3-hexafluoro-2,2_bis [4 ~ (3,4 dicarboxyphenoxy) benzene Group] propane dianhydride, etc. As for the diamine compound, aromatic diamine, heterocyclic diamine, and aliphatic diamine can be used. Examples of the aromatic diamine are as follows: p-phenylene diamine, m-phenylene diamine Amine, this paper scale is universal Chinese standard (CNS) A4 wash (210X297 mm) ^^ 1 11 ---- = n II ....... 1.- I: III _ (Please Read the notes on the back of the page before filling in this page) -25-A7 4 34 4 5 5 B7 V. Description of the invention (23) 1 p-xylyldiamine, m-xylyldiamine, 1, 5- Diamino, (Please read the notes on the back before filling out this page) benzidine, 3,3 dimethylbenzidine, 3,3 / _dimethoxybenzidine, 4, 4 — (or 3, 4 one, 3, 3 one, or 2, 4- one —) diaminodiphenylmethane, 4, 4- one-(or 3, 4 Mono, 3,3 >-, or 2,4 mono-) diaminodiphenyl ether, 4,4-mono (or 3,4-mono, 3,3 >-, or 2,4-mono) Aminodiphenylsulfone, 4,4-a- (or 3,4-a-, 3,3-a-, or 2,4-a-) diaminodiphenyl sulfide, 4,4-onebenzophenone Amine, 3,3 > phenone diamine, 4,4-bis (4-aminophenoxy) phenylhydrazone, 4,4 bis (4-aminophenoxy) biphenyl, Ministry of Economic Affairs Central sample bureau, Consumer Cooperative, Yindong 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,1,1,3, 3,3-hexafluoro-1,2-bis (4-aminophenyl) propane, 2,2-bis [4- (4-aminoaminophenoxy) phenyl] propane, 3,3 dimethyl Base-4,4 ——Diaminodiphenylmethane, this paper size is applicable to Chinese Standard (CNS) A4 Washer (210X297mm) -26-A7 4 34 4 5 5 B7 V. Description of the invention (24 ) '3,3 -—, 5,5-tetramethyl-4,4-diaminodiphenylmethane, 4,4 < -bis (3-aminophenoxy) phenyl, 3 , 3 2 Master diphenyl, 2,2 < - bis (4-aminophenyl) propane, and the like. Examples of heterocyclic amines are as follows: 2,6-diaminopyridine, 2,4-diaminopyrimidine, 2,4-diamino-s-tris, 2,7-diaminodibenzofuran, 2,7-diaminopyrazole, 3,7-diaminobenzoxazine, 2,5-diamino-1,3,4-thiadiazole, 2 '4-diamino-6- Phenyl-s-triazine, etc. Examples of aliphatic diamines are as follows: Trimethylene diamine, tetramethylene diamine, hexamethylene diamine, 2,2-dimethylmethylene diamine, diamines represented by the following formula Silyl: ch3 ch3 i 1 H2N—Si- Ο-Si — (-CH2-) ^-NH2

I I ch3 ch3 where n and m are the same or different integers 1 to 1 0. This paper size applies to China National Standard (CNS) A4 (2i × 297mm) (Please read the precautions on the back before filling out this page) 1 ^ -------- Order the Central Bureau of Standards, Ministry of Economic Affairs Printed by employee consumer cooperatives 27-4 3d 4 5 ο B7 Printed by the Central Government Standards Bureau, Ministry of Economic Affairs, Industrial Consumer Cooperatives, and printed on the 5 'Invention Description (25) t 1 1 Some of these tetracarboxylic dianhydrides and diamine compounds can be sold separately — Or use it as a mixture 1 | State 0 1 1 (Η) Cellulose esters I Please 1 J such as > Methyl serotonin ί Ethyl cellulose y weavin esters 0 Read 1 | Read by Adding an organic polymer with a molecular weight of 髙 to the photosensitive composition can improve the back surface I. Adhesion to the substrate 9 Chemical resistance > Film-forming properties J etc. 0 Note 1: I Add quantity should be 2 0 — 8 0% by weight 1 The total weight of the high-molecular-weight organic polymer and the addition polymerizable compound is based on the weight of the base. The standard (in terms of photocurability) 〇 t 1 I After adding the high-molecular-weight organic polymer to the photosensitive composition In the case! I 9 The amount of the photoinitiator composition used is the same as the amount of the photoinitiator composition 1 1 I (A) (B) or (C) used. 0 1 Order the photosensitive composition of the present invention A more ideal example is as follows: 1 1 (i) N — (p-monocyanophenyl) _glycine 7 7 —diethylamine 1 I — 3 —anilylcarbonyl-coumarin 9 bis (cyclopentane Alkenyl) — bis C! 1 2 J 6 — difluoroyl — 3 mono (pyrrole — 1 —yl) phenyl] titanium 9 (formyl J group) acrylic acid — 3 — dimethylaminopropyl ester and poly (fluorene Amino acid) (made by reacting 4 1 I 4 —diaminodiphenyl ether with pyromellitic dianhydride) 1 1 compound > 1 (ϋ) Ν — (p-methylsulfonylphenyl) -N -methylglycinic acid! Γ 9 7-diethylamino-3-succinocarbonyl-coumarin > 2, 6- Bi 1 1 (p-N 9 Ν-diethylaminobenzaldehyde) 4-methyl 1-4-azai 1 cyclohexanone (meth) acrylic acid-3-dimethylaminopropyl ester and poly (醯 1 1 Amino acid) (made from 4 4 diaminodiphenyl m and pyromellitic dianhydride 1 1 1 This paper size is applicable to China National Standard (CNS) Sixty-four Regulations < grid (210X297 mm) ) -28-A7 B7 V. Mixture of the description of the invention (26) ·) and (iii) 7 —diethylamino — 3 —hexylcarbonyl — coumarin, bis (cyclopentadienyl) — Bis (2,6-dicyano-3- (pyrrole-1-yl) phenyl] titanium, 1,3-diphenyl-1,2,3-propanedione 2- 2- (o-ethoxy) Carbonyl) oxime, dimethylaminopropyl methacrylate and poly (fluorenic acid) (made from 4,4 * · _diaminodiphenyl ether and pyromellitic dianhydride) Of a mixture. The photosensitive composition also contains (if necessary) 1 or more colorants (such as dyes, pigments, etc.). Examples of colorants are fuchsin, Crystal Violet, Methyl Orange, Seagrass Blue 2 B, Victoria pure blue, Malachite Green, Night Green B, Spilon Blue, and the like. In order to enhance the storage stability of the photosensitive composition, a radical polymerization inhibitor or a radical polymerization inhibitor may be added. Examples of the aforementioned inhibitors or blockers are p-methoxyphenol, p-benzoquinone, hydroquinone, pyrogallol, an amine, phenazine, arylphosphite, nitrosoamine, and the like. Printed by the Central Labor Bureau of the Ministry of Economic Affairs, Beige Consumers Cooperatives— (Please read the precautions on the back before filling out this page) The photosensitive composition of the present invention can be used as a photosensitive resin composition. In addition, the photosensitive composition of the present invention may contain one or more other additives such as a plasticizer, an adhesion promoter, and the like. The photosensitive material of the present invention includes: (a) a poly (fluorenic acid) such as described above, (b) having one or more carbon-carbon double bonds that can be polymerized or polymerized using actinic rays and 1 or more amines Base or its quaternary salt type compound, the aforementioned paper size is applicable to the Chinese standard (CNS) A4 (210X297 mm) -29-Printed by 434 A5, Beijiao Consumers Cooperative, China Ministry of Economic Affairs 5 A7 B7 5. Description of the invention (27) The compound is selected from the group consisting of addition polymerizable compounds having a boiling point of 100 ° C or higher (under atmospheric pressure), and (c) a photoinitiator composition (A), (B) or (C). Poly (amidate) (a) should preferably use an equimolar number (in the case of poly (amidate) carboxyl groups, relative to compound (b)). The photoinitiator composition (c) should preferably be used in an amount of 0.0 to 30% reset, more preferably 0. 05 to 10% by weight (based on the weight of the compound (b)). Ϋ́ Compound (b ) (That is, a compound having one or more carbon-carbon double bonds that can be dimerized or polymerized with actinic rays and one or more amine groups or their quaternary salts) is as follows: 0 Ϊ CH2 = CH-COCHzCHzN (ch3) 2 f 〇1 CH2 = CH-COCH2CH2CH2N (CH3) 2, ch3 0

I I CH2 = C— COCH2CHzN (CH3) 2, ch3 0

I I ch2 = c— COCH2CHzCH2N {CH3) 2, ch3 o

I II ch2 = c——COCH2CHzCH2CH2N (ch3) 2, 〇

II CH3-CH = CH-COCHzCH2N (CH3} 2, this paper size applies Chinese National Standard (CMS) AA specification (210X297 mm)! _ Ί-i Hi. I-------I-if · _ _ (Please read the precautions on the back before filling in this f) Book -30-434455 A7 B7 V. Description of the invention (28) 0 CH3-CH = CH-COCH2CHzCH2N (CH3) 2 / ο CH3-CH = CH- CH = CH-COCH2CH2N (CH3): 〇II CH3-CH = CH-CH = CH-COCH2CH2CH2N (CEz) Zi

0II C H = C H—COCH2CH2N [CH]] 2 The photosensitive material may include one or more bisman nitrogen compounds. Examples of double barrier nitrogen compounds are as follows: and so on. (Please read the notes on the back before filling out this page} N. 0

N, N.

0

CH

N. N.

Seal of Work and Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs 0

CH

N, N

〇

This paper music scale is in accordance with Chinese standards (CNS > AO see-through (210X297 mm) 31 4-3 4- 5 A7 B7

OH 0

C Η ^ Ο π

(Please read the notes on the back before filling out this page)-l-—i-1-- I I-1 --- 1 ^ 1 I- -I ί 一 交 ii—! -II TJ. ^ 1 ^ 1 Two, > ^ 2 Printed by the Offshore Consumers Cooperative of the China Standards Bureau of the Ministry of Economic Affairs

CN I C Hr: C-< 〇 > N.

I- ^ ------—— ^-I Applicable to China National Standards for each paper size (CNS > A4 now (2 丨 OX297mm > -32-V. Description of the invention (30) N-

Ν · ◎ A7 B7 ◎ 0

Ο CH

: CH

OK NT I COOC.H, 0

50, N., Etc. The amount of double azide compound used in the printing cage of the Central Working Group of the Ministry of Economic Affairs of the Ministry of Economic Affairs should be 0.01-10% of replacement (based on the weight of poly (amine) (a)). As the solvent of the photosensitive material, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, r-butyrolactone, and dimethylimide can be used. Samarium, iodoane, etc., or a mixture of at least one element selected from the group consisting of xylene, toluene, methyl ethyl ketone, diethyl ketone, and the like. The method for forming a pattern of the present invention includes coating a photosensitive material on a substrate. , Drying the photosensitive material will expose the photosensitive material, and then develop the photosensitive material to obtain the desired pattern. The size of this paper is applicable to China National Standard (CNS) Α4 specification (2 丨 0 ×: 297mm) 11 — 丨 — — --- ^ ------ order ---- iridium (please read it first) Note on the back, please fill out this page again) -33-Attachment H (A) Λ ο Λ 7r- r- Patent No. 83106688 4 34- 4- 〇b A7 r ~ ......... . ____Chinese description of damage repair ^ Page_ 民 _ 长 8 年 08 月 August revision: V. Description of the invention (31) -------- More specifically, the pattern formation is performed as follows: • Photosensitivity Materials are coated on substrates (such as silicon wafers, metallic substrates, glass substrates, ceramic substrates) * which use the dipping method, spray method, screen printing method, spin coating method *, etc. • Heat-drying removes most of the solvent to form a non-sticky coated film. • Place a mask with the desired pattern on the coated film and irradiate it with actinic rays. Examples of actinic rays are Ultraviolet light, deep ultraviolet light, visible light, electron beam, X-ray, etc. * After exposure * Unexposed parts are removed with a suitable developing solution to obtain the desired pattern. As for the developing solution, a good solvent can be used, such as N, N-dimethylformamide, N · N-dimethylacetamide * N-methyl-2-pyrrolidone, etc. and the like A mixture of a good solvent and a poor solvent (such as lower alcohols, water * aromatics, etc.) • After development, wash with a poor solvent (if necessary), and then dry at about 100 force to Stabilizing the case · The present invention is illustrated by examples. In the examples, all percentages are by weight unless otherwise specified. Example 1: Synthesis of N- (p-methylsulfonylphenyl) -N-methylglycine Acid (Compound 1) Put 4 monofluorophenylmethasone (15.01 g'86.26mmoles), N-methylglycine (8.45g * 94.89 mmoles) into a 50 OmJZ pear-shaped bottle And potassium carbonate (14. 2 8 g, 103 · 48mmoles) • With the addition of 120mjZ, two paper sizes are applicable to China National Standard (CNS) A4 (210 X 297 mm) < Please read the back first For legal matters, please fill out this page) _ III Order! 11! · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -34-4 344b 〇 A7 _ _B7___ V. Description of the Invention (32) · Methylasyl as a solvent. A water cooling tube was connected to the bottle and heated on an oil bath heated at 100 ° C to perform a reaction for 9 hours, while stirring with a magnetic stirrer. After leaving to cool, the reaction mixture was dissolved in 1 liter of water, and then hydrolyzed with 1/1 ON HCj ?, followed by filtering the precipitate. After thoroughly washing with water, the precipitate was washed with hexane / benzene (4/1 volume ratio). The yield of the dried product was 12.13 g (49.92 mraoles, 57.9%). Melting point is 161.2 ° C. Example 2: Synthesis of N- (p-fluorophenyl) -glycine (Compound 2) In a 50-OmJ? Three-necked flask, 4-cyanoaniline (10 Og, 8 4 7. 4 mmo 丨 es ), Followed by adding 300 μm β water and connecting a water cooling tube, a mechanical stirrer and a separatory funnel. The bottle is heated on an oil bath (printed in the Ministry of Economic Affairs of the Bureau of Quasi-Bureau Consumers Cooperatives (please read the precautions on the back before filling this page) at 100 ° C.) Into the bottle, monogasic acetic acid (104 g, 11 16 mmoles) was added dropwise within about 30 minutes of shovel, followed by heating and refluxing for 2.5 hours. After allowing to cool, add about 10 Omj? Ethyl acetate to the bottle to dissolve insoluble matter. Separate the organic mash with a separatory funnel. The residual aqueous layer was mixed with a water layer obtained by extracting the organic layer with a 10 OmJ? 5% (by weight) NaOH solution, followed by acid hydrolysis with 1/1 0 N HCi ?. The resulting precipitate was filtered and washed several times with water. After drying in an oven heated at 60 ° C for 3 hours, the dried precipitate was dried in an air dryer overnight. The resulting product was a yellow-brown powder, which had no melting point, but decomposed at 23,3.1 ° C. The yield was 38.8 g (2 6%). The paper size is applicable to China National Standards (CNS) A4 specifications (210 X 297 mm) -35-4 3445 5 A7 B7 V. Description of the invention (33) 1 Example 3: Synthesis of N— (p-cyanobenzene ) -N-methylglycine (Compound 3) In a 50 OmJ? Pear-shaped bottle, put 4-fluorophenylbenzyl (10.4.4g, 86.2. 6mmoles), N-methylglycine Amino acids (8.45 g '94.89 mmoles) and carbonic acid (14. 28 g, 103.48 mmoles) were added, followed by the addition of 20 OmJZ dimethylimine as a solvent. A water cooling tube was connected to the bottle and heated on an oil bath heated at 1000 ° C for 9 hours (while stirring with a magnetic stirrer). After leaving to cool, the reaction mixture was dissolved in 1 liter of water and acidified again with 1/1 ON HC, followed by filtering the sediment. After washing thoroughly with water, the sediment was washed with hexane / benzene (4/1 body ratio). The yield of the dried product was 14.21 g (74.79 mmoles, 86, 7%). The melting point is 64.5 ° C. The structures of Compounds 1 to 3 were confirmed by the η1-NMR spectrum shown in Table 1. (Read the precautions on the back before reading this page before filling in this page)-° i i. The work load of the Central Bureau of Standards of the Ministry of Economic Affairs «· Cooperation Du Printed This paper size is applicable to China National Standard (CNS) A4 (210X297) Centimeters) -36-5 5 4 4 3 4

A

7 B V. Description of the invention (34) 'Table 1 Chemical shift of printed compounds in the Consumer Cooperative Bureau of the Ministry of Economic Affairs, Proton Number, Proton Type Coupling Constant (Hz) 1 3. 00 (s) 3H CH3S〇3-Ar_- 3. 15 (s) 3H N-CHa-4. 11 (s) 2H n-ch2-c〇2h-6.73 (d) 2H Ar-H 9.03 7.72 (d) 2H Ar-H 8. 96 2 4.04 (d ) 2H HH2-c02h 5.20 6. 0 8 (s) 1H NH — 6. 78 (s) 2H Ar-H 8.80 7.47 (d) 2H Ar-H 8. 80 3 3.12 (s) 3H N-CHs- 4. 15 (s) 2H N-CHs-COsH-6.65 (d) 2H Ar-H 9. 09 7.49 (d) 2H Ar-H 9.10 The paper scale is free to use Chinese national rubbing (CNS) A4 wash grid (210X297 (Mm) -----! --- ^-(锖 Please read the precautions on the back before filling in this page) Ding- · α -37-Printed by the Shell Worker Consumer Cooperative of the Central Procurement Bureau of the Ministry of Economic Affairs-Λ 3d A5b Α7 Β7 V. Description of the invention (35), Examples 4 to 8, Comparative Examples 1 and 2: Photosensitive material is a mixture of 1 Og N — poly (amidate) (solid content of 20%) by stirring Methyl-2-pyrrolidone solution (the poly (fluorenic acid) is prepared by the reaction of isomolar 4,4 diaminodiphenyl ether with pyromellitic dianhydride ), 1 · 8g methacrylic acid, a 2 - dimethylamine ethyl methacrylate, and the light as shown in Table 2 of the initiator composition is made. After filtering with a filter, a photosensitive material is spin-coated on a silicon wafer. After heating on a 100 ° C hot plate for 200 seconds, the solvent was removed to obtain a photosensitive coating film. After drying, the film thickness was 1 and the photosensitive coating film was exposed through a photoprotective sheet (p h 〇 t 〇 m a sk) using an ultra-high pressure mercury lamp. The number of exposures was 50 OmJ / crrf. The obtained film was immersed and developed using a mixed solution of N-methyl-2-pyrrolidine and methanol (4/1, body weight ratio), and then washed with isopropyl alcohol. After development, measure and observe the pattern shape. The normalized film thickness (NFTAD) (the film thickness divided by the initial film thickness) after development and the minimum opening perforation diameter (opening diameter) are shown in Table 2. In Example 4 (where N- (p-methylsulfonylphenyl) -N-methylglycine was used for the film), the final curing film was heated at 100 t for 15 minutes, at It is obtained by heating at 20 ° C for 20 minutes and heating at 350 ° C for 60 minutes (in a nitrogen atmosphere). The film thickness of the final cured film is 5 ρ Π1, which has excellent polyimide roundness. As shown in Table 2, according to the data of NFTAD and the diameter of the opening, an evaluation result that the photosensitive material of the present invention has excellent resolution can be obtained. Therefore, the photosensitive material of the present invention has excellent photosensitive properties (and ratio- -: ---.--- A ------ IT ------ ^ (Please read the notes on the back before filling in this page) This paper size is applicable to China National Standards (CNS) Grid A4iii (210 × 297 mm) -38-Du Yinye 4 3445 5 A7 B7 Duties of Consumers and Consumers Cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the Invention (36) 'Compared with examples). (Please read the notes on the back of S1 before filling in this page) i Λ ------ Order ------ ^ ------: --- ^ — This paper size applies to Chinese national standards ( CNS) Α4 specification (210 乂 297 mm) -39-5 5 4 4 3 4 V. Description of invention (37) 'Table 2 Example number printed by the Central Consumers ’Association of the Ministry of Economic Affairs, Consumers Cooperatives, printed example number, comparative example, 4 5 6 7 8 1 2 DETC lOmg lOmg lOmg 0 0 lOmg 0 Detergent (AA) ACH 0 0 0 lOmg lOmg 0 lOmg Chemical decoration 1 lOOmg 0 0 lOOmg 0 0 0 Chemical Wei 2 0 lOOmg 0 0 lOOmg 0 0 Chemical impurities 3 0 0 lOOmg 0 0 0 0 m NFTAD (%) 98 97 98 96 99 65 0 Opening diameter (^ m) 8 8 8 8 8 10 Not any pattern Note) DETC = 7-N, N-diethylamine —3—Carbonyl-coumarin ACH = 2,6—bis (p—N, N_diethyl_benzaldehyde) —4-methyl-azacyclohexanone This paper is in accordance with China National Standards (CNS) ) A4 Washer (210X297mm) (read the notes on the back before filling out this page) • 40-4 3445 5 A7 B7 Printed by the Central Standard of the Ministry of Economic Affairs and Consumer Cooperatives V. Description of the Invention (38) 1 1 Example 9 — 1 4 Comparative Examples 3 — 5 1 1 N— (p-cyanophenyl 1 1) —glycine 0 i I was synthesized in the same manner as described in Example 2 — N — (p-cyanide Phenyl group please first M 1 1) — * N monomethylglycine 0pcj Read back I Photosensitive material is mixed by stirring 1 0 8 poly (pyramic acid) (Note 1 solid content 2 0 % 'It is made by the number of moles 4 4 —-amino diphenyl matter 1 Ι 1 1 ether reaction with pyromellitic dianhydride) 1 8 g methacrylic acid-fill% I 2 — * — Methylaminoethyl 9 and the photoinitiator composition (Page 1 1 B) shown in Table 3 to make 0 1 1 I. Patterning and measurement were performed in the same manner as described in Examples 4 to 8. Normalized film after development 1 1 The thickness (NFTAD) and the opening diameter are listed again in Table 3 and 0. In Table 3, the shape of the pattern is also listed. 1 1 As for the dry film 9 of Example 1 2 the final cured film is obtained at 1 0 0 1 Heating at 1 ° C for 15 minutes 9 Heating at 20 ° C for 20 minutes and heating at 1 1 3 50 ° C for 60 minutes (under nitrogen atmosphere). The thickness of the final cured I film was 10 μm. 9 It has a unique polyfluorene imine pattern. 1 1 As shown in Table 3 y According to the data of NFTAD and opening P diameter 9 I ί The evaluation result that the photosensitive material of the present invention has excellent resolution can be obtained> 1 Because of this, 9 The photosensitive material of the present invention has stupidity Photosensitive properties in comparative examples ί.) 1 i 1 1 1 1 ί This paper scale is applicable to the National Standard of China (CNS) A4 ^ grid (210 X 297 mm) _ 41 — Central Bureau of Standards, Ministry of Economic Affairs® Collaboration with Xiaoxian. Du Yin 4 34 4 5 5 A7 A7 B7 V. Description of the invention (39) 'Table 3 Example No. Example Comparative Example 9 10 11 12 13 14 3 4 5 Light-faced chick ⑻ BC 10mg 0 0 lOmg 10mg 0 lOmg; 0 0 MOBC 0 lOtDg 0 0 0 lOmg 0 0 0 DETC 0 0 lOmg 0 0 0 0 0 0 Ermao Drink 1 lOOmg lOOnig lOOmg lOOmg lOOmg lOOmg 0 lOOnig lOOnig Chemicals 2 0 0 0 lOOnig 0 lOOmg 100 mg 0 100 mg 3 0 0 0 0 100 mg 0 0 0 0 NFTAD (%) 78 77 78 96 99 95 60 25 25 Opening diameter (ίΜΙ) 8 8 8 8 8 10 20 100 100 SB case shape is good good good Good good tm swell swell) BC two 3, 3 one-several Bis (7-diethylaminocoumarin) M0BC = 3,3 one-to-one type of bis (7-metheudin) DETC = 7-N * N-diethylamino-3 ~ Ht —Coumadin dihetero 1 = dichlorodienyl) -bis [2,6-diminus-3- (sec-1-yl) phenyl] titanium paper paper scale Chinese National Standards (CNS) A4 * t cell (2 丨 Ox29 "? mm) (Please read the notes on the back before filling in this page) Order -42-434455 A7 B7 V. Description of the invention (4〇) I Example 1 5 — 2 0, comparative example 6 — 8: To the same photosensitive material used in Examples 9 to 14 and Comparative Examples 3 to 5 was added 2 Omg 4,4-a bisazido -3,3-dimethoxybiphenyl ( AZ) and the same test 0 as in Example 15-2 was performed. The results are shown in Table 4. As shown in Table 4, the evaluation results of the excellent resolution of the photosensitive material of the present invention were obtained based on the data of the NFTAD and the opening diameter, and the standardized film thickness after development was improved due to the addition of the biazide. (Please read the memorandum of the first note before filling in this page) '-β This paper is printed by the Central Ministry of Economic Affairs and the Junanan Employee Consumer Cooperative. The standard is applicable to China National Standards (CNS) 8 4 * See the grid (2 丨 0 X 297 mm) -43 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 4 34 4 5 5 a7 B7 V. Description of the invention (41) 'Table 4 Example number Example comparison example 15 16 17 18 19 20 6 7 8 BC lOrog : 0 0 lOmg lOmg 0 10? 0 0 U / jfrifAaiBrr MOBC 0 lOmg 0 0 0 lOmg 0 0 0 Thief (B) DETC 0 0 10 0 0 0 0 0 0 0 Titanocene 1 lOOmg lOOtBg lOOmg lOOmg lOOmg lOOmg 0 lOOmg lOOmg compound 2 0 0 0 lOOmg 0 lOOmg l100mg 0 100 beer 3 3 0 0 0 0 lOOmg 0 0 0 0 _ AZ 20mg 20mg 20mg 20mg 20? 20mg 20mg 20mg 20mg NFTAD (%) 85 85 85 100 100 100 65 30 30-year-old opening diameter (μm) 8 8 8 8 8 10 20 100 100 The pattern is fine, good, good, good and good.

、 1T This paper size is applicable to China National Standards (CNS) A4 (210 X Μ7 mm) -44 Printed by the Central Consumer Standards Bureau, Ministry of Economic Affairs, Consumer Work Cooperatives 4 34 4 5 5 ΑΊ __ _Β7_ V. Description of the invention ( 42) 'Examples 2 1-2 6 and Comparative Examples 9-1 4: Photosensitive materials are mixed by mixing poly (Enzyme Amino Acid) (solid content is 20%, set by the equal mole number to 4, 4 / —Diaminodiphenyl ether and pyromellitic dianhydride made by reacting) 10 g of N-methyl-2-pyrrolidone solution, 1.8 g of 2-dimethylaminoethyl methacrylate And the photoinitiator composition (C) shown in Table 5. The pattern was formed in the same manner as described in Example 4-8, and the thickness of the normalized film (NFTAD) and the diameter of the opening after the temporal shadow were measured, and are shown in Table 5. In Table 5, the shapes of the patterns are also listed. As for the dry film of Example 24, the final curing film was heated at 100 ° C for 15 minutes, heated at 200 ° C for 20 minutes, and then heated at 3 50 ° C for 60 minutes. (Under a nitrogen atmosphere). Finally, the film thickness of the heating film is 10, which has an excellent polyimide pattern. As shown in Table 5, based on the data of NFTAD and the diameter of the opening, the evaluation result of the photosensitive material of the present invention having excellent resolution can be obtained. Therefore, the photosensitive material of the present invention has better photosensitive properties than the comparative example. 0 ( (Please read the notes on the back before filling out this page)

A 3-foot rule paper SNC / 1- I quasi-household country 55Λα43 07 V. Description of the invention (43) 'Table 5 Case study of cooperation with shellers in the Central Standards Bureau of the Ministry of Economy 9 10 Π 12] 3 14 Thief CC) BC lOzs? 0 0 lOmg ΰ 0] 〇mg lOmg 0 0 0 0 M0BC 0 lOatg 0 0] 〇π «0 0 0 0 0 0 DETC 0 0 ΙΟπκ 0 0 0 0 0 0 0 0 Er Mao 1 lOOmg lOOieg lOOrag lOOsog lOOmg lOOmg 0 0] 00mg lOOmg lOOmg lOOmg lOOmg S56S1 lOOne lt) te 10te lOOmg iOOmg lOOmg lOOmg 100m 0 0 lOOmg lOOrag Additive AZ 0 0 0 20mg 20mg 2 0m 0 2 〇aig 0 2〇m 0 20mg NFTAD (%) 75 75 75 85 S5 85 60 65 25 30 25 30 30 Opening diameter (P Γ) 10 10 10 10 10 10 10 20 20 100 100 100 100 Drawing dish 犾 MF cake gambler Pie notch Xiakou viscera grade mm surface Note) Touch 1 = 1, 3-2, 1, 2, 3 said trione 1-2-(0-ethoxypoly) oxime This paper is applicable to the China National Standards (CNS) ) Α4 specification (2! 0 × 297 mm) (Please read the notes on the back before filling this page) Order 46

Claims (1)

4 34 4 5 5 A8 B8? C8 I D8 丨 VI. Patent Application or Attachment (A): Supplement No. 83106688 Patent Application Chinese Patent Amendment Scope Amendment September 1989 Amendment 1 The photo-initiator is an N-aryl-α-amino acid represented by the following formula (I), and when used in combination with one or more appropriate photosensitizers, an active group can be generated by the action of ultraviolet light or visible light : 〇r3 Π7I IN——C——COOHI .ns ps In the printed format of the Consumer Cooperatives of the 4th Bureau of the Ministry of Economic Affairs, the consumer cooperative: R '»R a, R 4 and R 5 each indicate a hydrogen atom; Ra indicates a cyano group or (Ci_4) alkylsulfonyl group; Re indicates a hydrogen atom or (Ci_4 ) Alkyl; and R · / and R8 each represent a hydrogen atom. 2. A photoinitiator composition (A), comprising: (a) N-aryl-α-amino acid represented by the formula: D R. Α 7 N-C-COOH I R8 (r) In the formula: R i 'R 2 and R respectively represent hydrogen atoms; r 3 represents a wheel group or (Cbl) alkanesulfonyl group; R6 represents a hydrogen atom or (Cl-4) winding group. And this paper scale applies to China National standard (CNS M4 specification (210X297 mm) I -------.---- installation ------ order ------ line (please read the notes on the back * before filling in (This page) Printed by the Ministry of Economic Affairs, Intellectual Property, and Employee Consumer Cooperatives. 4 34 4 5 5 as C8 _______ DS 々, the scope of patent application, and r8 each show a hydrogen atom, (b) at least one selected from 7 — N, N-2 Ethylamino-3-Kettenyl-coumarin (DETC), 3,3 > -Pseudobis (7-diethylaminocoumarin) (BC) or 3,3 < monocarbonylbis (7 — methoxycoumarin) (MOBC), and (c) 2 '6 —bis (p-n' N —diethylaminobenzaldehyde) — 4 monomethylmonoazahexanone (ACH ), Wherein the compound (b) or (c) is used in an amount of 1 to 30 parts by weight per 100 parts by weight of the compound of the formula (I-). 3. A photosensitive composition comprising: Can be selected from acrylate or methacrylate, vinylbenzene or acrylamide Addition polymerized compounds having a boiling point of 1000 ° C or higher at 1 atmosphere pressure, and a photoinitiator composition (A) as described in item 2 of the patent application scope, The content of A) is from 0.05 to 10% by weight based on the weight of the addition polymerizable compound. 4. The photosensitive composition according to item 3 of the patent application scope, further comprising one or more selected from the group consisting of High molecular weight organic polymer of polyester, vinyl polymer, polyoxymethylene, polyurethane 'polycarbonate, polyamidine, poly (amidoic acid) or cellulose ester. 5 * —a photosensitive material, which Contains: (a) 100 parts by weight of poly (fluorinated acid), (b) 100 parts by weight of carbon-carbon double bonds having 1 or more dimerization or multimerization using actinic rays and i Or more amines or their quarterly paper size suitable for the financial axis to M⑽ 丨 (MM297 public director) ---------- installation ------ order ------ line (please (Please read the notes on the back before filling out this page) 2 4 3445 5 A & B8 C8 D8 VI. Patented compounds for salts and (c) 0.05 to 10 parts by weight as claimed Please refer to the photoinitiator composition (A) in the second item of the patent scope. 6. If the photosensitivity material in the fifth item of the patent application, it also contains 1 or more bisazide compounds ° 7. The photosensitive material according to item 5 of the patent, which is used to form a pattern * 8. A photoinitiator composition (B), which includes: (a) N-aryl-α- Amino acid: (Please read the notes on the back before filling this page) In the formula, R 1 C is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and r2, r4 and hydrogen atoms are shown; r3 is cyano or () alkylsulfonyl: Re is hydrogen atom or (Cb) alkyl; R7 and R8 each represent a hydrogen atom, (b) at least one selected from the group consisting of 7-N, N-diethylamino-3--umylcarbonyl-coumarin (DETC), 3,3 carbonylbis (7- Diethylamine coumarin) (BC) or 3,3 carbonylbis (7-methoxycoumarin) (M0BC) (c) bis (cyclopentadienyl) one pair [2,6-difluoro Group_3 mono (pyrrole-1-yl) phenyl] titanium (titanocene 1), wherein for every 100 parts by weight of the compound of the formula (I <), the compound (b) ) A4 specification (210X297 public §) A8 B8 C8 D8 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. The amount of patent application) is 1 to 30 parts by weight, and the amount of the compound (C) is 50 To 200 parts by weight. 9. A photosensitive composition, comprising: an additive selected from the group consisting of propionate or methacrylate, vinylbenzene or acrylamide, having a boiling point of 100 ° C or higher at 1 atmosphere pressure. Polymerization compounds, and as the photoinitiator composition (B) of the scope of the patent application No. 8, the content of the photoinitiator composition (B) is 0 based on the weight of the compound of the addition polymer. 0 to 10% by weight. 10. The photosensitive composition according to item 9 of the scope of patent application, further comprising one or more selected from the group consisting of copolyester, vinyl polymer, polyoxymethylene, polyurethane, polycarbonate, polyamide, High molecular weight organic polymer of poly (amino acid) or cellulose ester * 1 1 · A photosensitive material comprising: (a) 100 parts by weight of poly (amino acid) (b) 1 〇〇 Replacement of compounds having one or more carbon-carbon double bonds that can be dimerized or multipolymerized using actinic rays and one or more amine groups or their quaternary salts, and (c) 〇.〇5 至10 heavy logic: parts of the photoinitiator composition (B) as claimed in item 8 of the scope of patent application 1. 2. As the photoactive material of the scope of application for item 11 of the patent scope, it also contains 1 or more phenyl groups Substituted Biazide Compounds · 1 3. For example, the photosensitive material for patent application No. 11 is used to form a pattern "4 3445 5 (Please read the precautions on the back before filling this page) This paper Standards are applicable t 蹰 «Family Standards (CNS) A4 (210X297 mm) -4 — Annex-Patent No. 831〇6688 is specified in Chinese Application for amendment page dated July 21, 1983 Case No. 83106688 Category ^ F (The above columns are filled by this Office) Miner 85 Check January I »Mill1 11 ^ W ~ 1 II I * — m < A4 C4 434455 Member of the Central Procurement Bureau of the Ministry of Economic Affairs X. Printed by the Consumer Cooperative II Patent Specification Invention I. New name Chinese formula (I) of N-fluorenyl-0t-amino acid, containing its photoinitiator composition, containing light Photosensitive composition and photosensitive material of the initiator composition, and the way to form a picture with the photosensitive material in English ~ '_ ~ " N ^ aryl- -amino acid of the formula (I) »photoinitiator compositions comprising the same, photosensitive —L umpua ί UL Ull ~~ wQ—pnOLOS ^ nS ί ΐί X ~~ Πΐ8ίΐ »ΘΓί & t ~ COWPr lb 1 ^ Name! 1) Koji Masayoshi (2) Kojima Kojima (31 Katogi Momoki Nationality ⑴ Japan (2) Japan (3 Japan. Inventor 1. The creator (1) Japan, 206, Taiyuan-cho, Hitachi City, Japan, dwelling place (2) Japan, Ibaraki Prefecture, Higashi-machi, Hitachi City 4_2_9 (3 ) Higashi-cho, Higashi-cho, Hitachi, Ibaraki Prefecture 219 ____ Name (Name) (1) Hitachi Chemical Industry Co., Ltd. 'Hitachi Chemical Industry Co., Ltd. Nationality (1) Japanese three, applicant's residence, domicile (office) (1) Niigata, Nishi Shinjuku, Shinjuku-ku, Tokyo, Japan Name of the representative of Yifan No.1 (1; Dan Yeyi This paper size applies to China National Standard (CNS) A4 specification (210 X 297 public #)) Annex H (A) Λ ο Λ 7r- r- Patent No. 83106688 Patent Case 4 34- 4- 〇b A7 r ~ ................. ____ Chinese description of damage ^ page_ 民 _ 久 8 年 08 August revision: V. Description of the invention (31)- -—---— More specifically, the patterning is performed as follows: • A photosensitive material is coated on a substrate (such as a silicon wafer, a metal substrate, a glass substrate, or a ceramic substrate). It uses the dipping method, spray method, screen printing method, spin coating method *, etc. • Removes most of the solvent by heating and drying to form a non-slip coating film. Mask of pattern and irradiated with actinic rays. Examples of actinic rays are ultraviolet light, deep ultraviolet light. Visible light, electron beam, X-ray, etc. * After exposure * Unexposed parts are removed with a suitable developing solution to obtain the desired pattern. As for the developing solution, a good solvent can be used, such as N, N-dimethylformamide, N · N-dimethylacetamide * N-methyl-2 2-pyrrolidone, etc. and the like A mixture of a good solvent and a poor solvent (such as lower alcohols, water * aromatics, etc.) • After development, wash with a poor solvent (if necessary), and then dry at about 100 force to Stabilizing the case · The present invention is illustrated by examples. In the examples, all percentages are by weight unless otherwise specified. Example 1: Synthesis of N- (p-methylsulfonylphenyl) -N-methylglycine Acid (Compound 1) Put 4 monofluorophenylmethylshusone (15.01 g '86 .26mmoles), N-methylglycine (8.45g * 94.89 mmoles) into a 50 OmJZ pear-shaped bottle And potassium carbonate (14. 2 8 g, 103 · 48mmoles) • With the addition of 120mjZ, two paper sizes are applicable to China National Standard (CNS) A4 (210 X 297 mm) < Please read the back first For legal matters, please fill out this page) _ III Order! 11! · Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-34-434455 A5 B5 Chinese Abstract of Invention (Name of the Invention: Photoinitiator Composition and Use of Photosensitive Material of the Same) -Amino acid (I Ying compound), 3-Photoinitiator composition of substituted coumarin (Π) and azabenzaldehyde cyclohexanone (ΙΠ) < AN -aryl-π —Amino acid (or containing 3—substituted coumarin ([I) and dimocene: (titanocene) (IV) photoinitiator composition (β) and 3—substituted coumarin (II) ), The photoinitiator composition (C) of titanono (IV) ester (V) can effectively improve the photosensitivity of photosensitive materials containing polyamic acid) and addition polymerizable compounds used to form patterns. Central Ministry of Economic Affairs Printed by the Work Station Consumer Cooperatives -: --_---------- Shang ------ Order ----- line- ·-* '(Please read the notes on the back first and then fill in each page on this page. Shed) Private paper standards are applicable to Chinese National Standards (CNS) A4 specifications (2) 0 × 297 mm 4 4 4 5 5 A8 B8? C8 I D8 丨 Applicable patents or attachments (A): Supplement No. 83106688 Patent Amendments to the scope of the Chinese application for patents in the Republic of China in September 89. 1. An N-aryl-α-amino acid represented by the following formula (I) used as a photoinitiator is When multiple appropriate photosensitizers are used in combination, active groups can be generated by the action of ultraviolet or visible light: 〇r3 Π7I IN——C——COOHI .ns ps In the printed format of the Consumer Cooperatives of the 4th Bureau of the Ministry of Economic Affairs, the consumer cooperative: R '»R a, R 4 and R 5 each indicate a hydrogen atom; Ra indicates a cyano group or (Ci_4) alkylsulfonyl group; Re indicates a hydrogen atom or (Ci_4 ) Alkyl; and R · / and R8 each represent a hydrogen atom. 2. A photoinitiator composition (A), comprising: (a) N-aryl-α-amino acid represented by the formula: D R. Α 7 N-C-COOH I R8 (r) In the formula: R i 'R 2 and R respectively represent hydrogen atoms; r 3 represents a wheel group or (Cbl) alkanesulfonyl group; R6 represents a hydrogen atom or (Cl-4) winding group. And this paper scale applies to China National standard (CNS M4 specification (210X297 mm) I -------.---- installation ------ order ------ line (please read the notes on the back * before filling in (This page)