TWI295281B - - Google Patents

Description

1295281 A7 B7 __ V. INSTRUCTION DESCRIPTION (/) The present invention relates to a novel anthracene derivative, a chemically amplified photoresist composition comprising the same, and a use of the compound as a latent acid, which can be K actinic electromagnetic Activated by radiation and electron beam irradiation. In the case of U S4 54 0 5 9 8 , it is disclosed that K-sensitive oxime sulfonate compounds, such as 4-chloro-trifluoro-p-benzoquinone sulfonate, and traditional acid-hardenable resins are based. The surface is coated with a composition. In the case of US Pat. No. 4,736,055, 2,2,2-trifluoro-l-phenyl-ethanone oxime-(4-hydroxyphenylsulfonate) is disclosed as a polymer which can be used for a positive photoresist resin. One ingredient. In U.S. Patent Nos. 5,620,1,1, and 5,759,740, the disclosure of the use of α-(4-tolylsulfonate-oxyimine)- 4-methoxybenzyl cyanide and α-(4-toluenesulfonate)-3 —Thienyl methyl cyanide is used as a latent acid supply for chemically amplified positive and negative photoresists at wavelengths of 340 to 390 nm, especially those that cause mercury i-rays (365 nm). It is disclosed in GB 2 3 6 6 58 that the use of a sulfonate as a latent acid supply in positive and negative photoresists in the wavelength range of 1 80 and 600 nm, especially at wavelengths exceeding 3 90 nm, is disclosed. region. Non-aromatic α-(alkylsulfonyloxyimine)-1-cyclohexenylacetonitrile and cx-(alkylsulfonyloxyimine)-1-cyclopentene acetonitrile are disclosed in U.S. Patent No. 5,147,625. A photolatent acid generator using a concentration of about 25 % of an oxime sulfonate compound as a non-chemically amplified positive photoresist is disclosed in Ε 24 1 42 3 . In Chemical Abstracts No. 97: 144503, 7 8 : 9 7 7 5 2, Synthesis (1 9 9 5 ), 5 5 3, revealing some fluoroketone sulfonate-5- paper scales applicable to Chinese national standards (CNS) A4 size (210 χ 297 mm) (Please read the note on the back and fill out this page) Order--------- Line 1 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1295281 A7 B7 V. Description of the Invention (>) Ester compounds are used as experimental products for synthetic studies. There is therefore a continuing need in the art field, particularly thermally stable and chemically stable reactive nonionic latent acid supply agents which can be used as K-, u-V-ray, X-ray or electron beam activation, and can be used as various acids. Catalysts for catalytic reactions, such as polycondensation reactions, acid-catalyzed depolymerization reactions, acid-catalyzed electrophilic substitution reactions or acid-catalyzed protecting group removal reactions. Particularly desirable is the latent acid catalyst with high stability or good solubility in the field of chemically amplified photoresists. Surprisingly, it has been found that special anthracene derivatives (as described below) are particularly suitable for the above acid-catalyzed reactions. catalyst. The spectral absorption range of the specific compounds of the present invention is particularly adjustable in the broad range of the electromagnetic wave spectrum, and is particularly suitable for use in the deep UV region. In addition, the ruthenium-containing chemically amplified photoresist composition of the present invention is thermally stable, even at high baking temperatures during processing, and provides a very high speed of light. Thus, the present invention relates to a chemically amplified photoresist composition comprising: (a) a compound which hardens under the action of an acid, or a compound whose solubility increases under the action of an acid; and (b) as a light sensitive At least one compound of formula I, II or III of acid supply, this paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page) -I I-- I--订-------1-line· Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 1295281 V. Invention description (

Wherein: R ί is hydrogen, unsubstituted C χ - C i 2 alkyl; ci-C iz alkyl is substituted by C 3 — C 3 fluorenyl fluorenyl; or Ri is C 3 — C 3 〇 cycloalkyl , Ci-C8 halogenated alkyl, C2-CH2 alkenyl, C4-C8 cycloalkenyl, C6-Ci zbicycloalkenyl, camphoryl; phenyl, unsubstituted or one or more Cl Ci 2 alkyl 'Ci-C4 dentate alkyl 'phenyl-Ci- 〇 3 fluorenyl, dentate, phenyl, OR4, NRs Rs, SR7, S0R7, and / or SO2 R7 substituted; substituent 0R4, SR7 and NRs R6 are optionally formed via R4, R5, Rs and/or Size 7 and other substituents on the phenyl ring, or together with a carbon atom on the phenyl ring to form a 5- or 6-membered ring; or Ri is Naphthyl, anthracenyl or phenanthryl, wherein these naphthyl, anthracenyl and phenanthryl groups are unsubstituted or via Ci-C6 alkyl, phenyl, hydrazine R4, NR5R6, SR7, SOR7 and/or S02 Substituted by R7; substituents 0R4, SR7 and NRs Re are selectively via r4 '5, Re and/or R7 and other substituents on the naphthyl, anthracenyl or phenanthryl ring, or with naphthyl, fluorenyl Or one on the Philippine ring Carbon atoms together form a 5 - or 6 - membered ring; ϋ paper size with this Chinese National Standard (CNS) A4 size (210 X 297 mm)

1295281 A7 B7 V. INSTRUCTION DESCRIPTION (4) or Ri is a heteroaryl group which is unsubstituted or consists of Ci-C6 alkyl 'benyl' OR4 * NR 5 R 6 9 SR 7 * S 0 R 7 , And / or S02 R7 substituted; the substituent 〇r4, SR7 and NRsRs are selectively via R4, Rs, uldent 6 and/or uldent 7 and other substituents on the heteroaryl ring, or on the heteroaryl ring One carbon atom together form a 5- or 6-membered ring; wherein all of the substituents Ri (except hydrogen) may be additionally bonded by having a 0-C bond or a 0-S i- bond, which will be cleaved under the action of an acid; R 7 ^ is phenylene, naphthalene, (please read the note on the back first to write this page)

Diphenylene or oxydiphenyl, wherein the substituents are unsubstituted or substituted by Ci-Ciz alkyl; or R'i is Ci-Ciz alkylene, or

A-A Factory A

The Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing A is a 0 -, a S -, - NR4 -, a 0 (CO) one S (C 0) one, one NR4 (C 0) one, one SO -, One S〇2 - or one 〇S〇2 -; Α! is interrupted by Ci-C12 alkylene or C2-C or multiple one-0; -8 ~ This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 2 alkylene, which is medium [295281 A7 B7 5. Inventive Note (Night) R 2 is R 3 is 醯, 樟C i 2 sulfonyl C 3 alkane halogen or C i - C i 〇 halogenated alkyl; Ci-Ci 8 alkylsulfonium, Ci-Ci 〇 halogenated alkyl sulfosulfonyl, phenyl-Ci-C3 alkylsulfonate, C3 - cycloalkylsulfonate, phenylsulfonate Anthracene, naphthylsulfonium, fluorenylsulfonyl or phenanthrene, wherein C3 - Ci2 cycloalkylsulfonium, phenyl-Ci-sulfenylcycloalkyl

a cycloalkyl group of a phenylsulfonyl group, a phenyl group, or one or more halogens, C 醢, naphthyl sulfonium fluorene, fluorenyl sulfonium sulfonate and phenanthryl sulfonaphthyl, an anthracenyl group and a phenanthryl group are unsubstituted, » C 1 , C 0 R 7 0 or R 3 group, one C 1 6 0 R 7 , S 0 2 one is C 2 - i-C4 halogenated alkyl, CN, N〇2 alkyl, phenyl, C a C4 alkyl sulfide, 0R4 Ci-C4 alkyl-(0C)0-, and/or a NR 5 R 6 substituted; C6 halogenated alkyl fluorenyl, halogenated benzamidine, or II1 -P- RaI 8 R〇L. Or (please read the notes on the back and fill out this page) Y2~R9 ΙΓ—P-Y3-R1C υ.—rq Ministry of Economic Affairs Intellectual Property Bureau Employees' Consumption Cooperatives Printed Υ i and Υ3 are not related to each other. SR / 3 is phenyl disulfonate, naphthalene disulfonate, this paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 —- __B7_ 5. Description of the invention (彡) Diphenyl sulfonium dioxime, or oxydiphenylene disulfonium, wherein these substituents are unsubstituted or substituted by Ci-Ci 2 alkyl; or RZ 3 is C2 — C12 alkyl disulfonium X is halogen; R4 is hydrogen, phenyl, Ci-Ci 8 alkyl, which is unsubstituted or derived from phenyl, OH, Ci-Cl2 alkoxy, C2-Cl2 alkoxy Carbonyl, phenoxy, phenoxycarbonyl, phenylsulfo*phenylthiocarbonyl, NR 5 R 6 , Ci-Ci2 alkylsulfonium, phenylsulfonyl, (4-methylphenyl)sulfonate and / or C2 - C6 alkyl fluorenyl substituted; or R4 is C2 - Ci 8 alkyl, which is interrupted by one or more 〇 - and it is unsubstituted or by benzene Base, OH, Ci-Ct 2 alkoxy group C2-Ci 2 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenyl sulfide, phenylthiocarbonyl, NRS R6, Ci-Ci2 alkylsulfonate , phenylsulfonyl, (4-methylphenyl)monosulfonate and/or substituted by C 2 -C 6 alkyl fluorenyl; or R 4 is C 2 -Ci 8 alkyl fluorenyl, which is unsubstituted or Phenyl, OH, Ci - C ^ 2 alkoxy, C 2 - Ci 2 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenyl sulfide, phenylthiocarbonyl, NR 5 R 6 , Ci-Ci2 Alkylsulfonium, phenylsulfonyl, (4-methylphenyl)monosulfonate and/or substituted by C2-C6 alkyl fluorenyl; or R4 is (:1 -Ci 8 alkyl sulphur, which is Unsubstituted or by phenyl, 0!·!, (:! alkoxy, C2 - alkoxycarbonyl-10- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) ( Please read the notes on the back and fill out this page.)

Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1295281 A7 ______B7 _ V. Description of invention (7) base, phenoxy, phenoxycarbonyl, phenyl sulfide, phenylthiocarbonyl, NR 5 R 6 , C i C i 2 alkylsulfonium, phenylsulfonyl, (4-methylphenyl)monosulfonate and/or substituted by C 2 -Cs alkyl fluorenyl; or R 4 is phenylsulfonyl, or (4- Methylphenyl) sulfonate;

Rs and R6 are each hydrogen-free or Ci-Ci 8 alkyl, which is unsubstituted or derived from phenyl, OH, Ci-C4 alkoxy, C2-C i 2 alkoxycarbonyl, phenoxy Base, phenoxycarbonyl, phenyl sulfide, phenylthiocarbonyl, phenylamino, phenylaminocarbonyl, Ci-2 alkylsulfonate, phenylsulfonate, (4-methylphenyl)- - 醯 and / or substituted by Ci - C6 alkyl fluorenyl; or Rs and Re are C2 - Ci 8 alkyl, which is interrupted by one or more 0 - and which is unsubstituted, Or by Ο Η, C i - C 4 alkoxy, C 2 - Ci 2 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenyl thio, phenylthiocarbonyl, phenylamino, phenylamino Carbonyl, Ci-Cl2 alkylsulfonium, phenylsulfonyl*(4-methylphenyl)monosulfonate and/or substituted by Ci-C6 alkyl fluorenyl; or R5 and is (:2 - Ci 8 alkane Anthracenyl, which is unsubstituted or derived from phenyl, OHfCi-Ciz alkoxy, C2-Cl2 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, benzene Amino group, phenylaminocarbonyl, Ci-Ci 2 alkylsulfonate, benzene Sulfonium, (4-methylphenyl)monosulfonate and/or substituted by C2-C6 alkyl fluorenyl; or Rs and Re are Ci-Ci 8 alkylsulfonyl, which is unsubstituted -11- This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -!1 Order ------I--line (please read the notes on the back and fill out this page)

«· A7 B7 1295281 V. Invention description (/ ) -------------- Installation ·-- (Please read the note on the back H to write this page) or by phenyl, 0H , C l — Ci 2 decyloxy, C 2 — Ci 2 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenyl thio, phenylthiocarbonyl*phenylamino, phenylaminocarbonyl, Ci _cl2 alkylsulfonium, phenylsulfonyl, (4-methylphenyl)monosulfonate and/or substituted by C2-C6 alkyl fluorenyl; or Rs and Rs are phenyl, benzhydryl, phenyl Sulfonium, (4-methylphenyl) sulfonium, naphthylsulfonium, decylsulfonyl or phenanthrylsulfonate; or R5 and 1^6 together with the nitrogen atom to which they are bonded form a 5-, 6 — or 7 — elementary ring, which may be interrupted by a 0 — or by an NR 4 —; R7 is hydrogen, phenyl, Ci — Ci 8 alkyl, which is not Substituted, or by phenyl, OH, Ci-Ci 2 alkoxy, C2 - Ci 2 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR5R6, Ci C12 alkylsulfonium, phenylsulfonyl, (4-methylphenyl)monosulfonate / or substituted by (32-〇6 alkyl fluorenyl; or R7 is C2 - Ci 8 alkyl, which is interrupted by one or more 0-, and which is unsubstituted or phenyl , OH, Ci-Ci 2 alkoxy, C2 - Ci z alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenyl sulfide, phenylthiocarbonyl, NR5R6 · C 1 ~ C ! 2 alkane sulfonate醯, phenylsulfonyl, (4-methylphenyl)monosulfonate and/or substituted by C 2 -C 6 alkyl fluorenyl; or R 7 is C 2 - Ci 8 alkyl fluorenyl, which is unsubstituted Or by phenyl, OH, Ci-Cl 2 alkoxy, C 2 -C 2 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenyl sulfide, phenylthiocarbonyl, -12- paper scale Applicable to China National Standard (CNS) A4 Specification (210 X 297 mm) ~~ 1295281 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 5, Invention Description (彳) NRsRs, Ci-Ci2 alkylsulfonate, phenyl Sulfonium, (4-methylphenyl)monosulfonate and/or substituted by Cz-Cs alkyl fluorenyl; or R7 is Ci-Ci8 alkylsulfonium, which is unsubstituted or derived from phenyl, OH, Ci-Ci2 alkoxy, C2 Cl2 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenyl sulfide, phenylthiocarbonyl, NR 5 R β , Ci-Ci2 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) a sulfonium sulfonate and/or substituted by a C2 - Cs alkyl fluorenyl group; or R7 is a phenyl sulfonium sulfonate or a (4 methyl phenyl) sulfonium sulfonate; R8, R9 and Ri 〇 are not related to each other by Ct a C6 alkyl group which is unsubstituted or substituted by halogen; or Rs, Rs and Rr〇 are phenyl which is unsubstituted or substituted by C i -C 4 alkyl or halogen; Or R9 and Ri 〇 are 1,4-phenylene or C2-C6 alkylene which is unsubstituted or substituted by Ci-C4 alkyl or halogen. The compounds of formula I, II and III are characterized by comprising at least two halogen atoms on one of the carbon atoms of the adjacent fluorenyl group. Preferably, the compound contains three halogen atoms on one of the carbon atoms of the adjacent fluorenyl group. The Ci-Ci 8 alkyl group is linear or branched, and examples are Ci - C8 -, Ci - Ce - or Ci - C4 alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4 Pentyl, 2-ethylhexyl, octyl, decyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and ten Octane•13· This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the note on the back page U first) Binding·· .线. 1295281 A7 B7 Ministry of Economics Intellectual Property Bureau employee consumption cooperatives printed five, invention description (π) basis; preferably Ci - 4 alkyl, like methyl, isopropyl or butyl. Cji-C8 alkyl, Ci-(:6-alkyl and Ci-C4-alkyl are also straight-chain or branched--like, for example, as defined above to the appropriate number of carbon atoms. Among them, the example of Li is Ci C8 - 'especially Ci-C6-, preferably Ci-C4-monoalkyl, like methyl or butyl. Examples of Rl are C2 - Ci2 - 'C4-Ci2-, C8-Ci-C4-C4-C8- Alkyl. C2 - Ci 2 alkyl, which is one or more times from a zero, for example, from non-conformity - 0 - interrupted from one to five times, such as one to three times or once or twice. Therefore, the resulting structural unit is: a 0(CH2)2〇H , - 0 ( C Η 2 ) 2 0 C Η 3 , -0 (CH2 CH2 Ο) 2 CHz CHs, a CH2 - 0 - CH3 , a CHzCHz- O - CH2CH3 , a [CH2CH2〇]y - C Η 3 , where y = 1 - 5, -(CHzCHzOisCHzCHs, a CH2CH (CHs) 0 C Η 2 CH e C Η 3 , or a CHz CH (CH3 ) - 0 - CHz - CH3 0 C3 — C3 〇cycloalkyl is a mono- or polycyclic aliphatic ring, such as a mono-, di- or tri-cyclic aliphatic ring, such as C3 - C2 〇-, - C! 8 -, C3 - Ci2 - , C3 — Cl0 ring Examples of alkyl groups, monocyclic rings are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or cycloheptyl, -14- The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). (Please read the notes on the back to write this page) ^ Order: Line - Ϊ295281 Α7 5, invention description (丨丨) Especially cyclopentyl and cyclohexyl. Examples of polycyclic structures are full hydrogenation, full hydrogenation Phenyl, fully hydrogenated, fully hydrogenated fluoroalkenyl, perhydrochrysenyl, perhydropicenyl, adamantyl, bicyclo[1 ·1 ·1]pentyl, bicyclo[ 4·2 · 2] fluorenyl, bicyclo [2·2·2] octyl, bicyclo [3·3·2] fluorenyl, bicyclo [4 ' 3 · 2] undecyl, bicyclo [4 · 3 · 3] dodecyl, bicyclo [3 · 3 ♦ 3] undecyl, bicyclo [4 • 3 · 1] fluorenyl, bicyclo [4·2·1] fluorenyl, bicyclo [3 · 3 · 1] Indenyl, bicyclo[3 · 2·1]octyl and analogs. In the present specification, the definition of C3 - C3 indole cycloalkyl also includes the indole cycloalkyl compound, such as spiro[5 ♦ 2] octyl Base, screw [5 · 4] sulfhydryl, spiro[5·5]undecyl. Further examples of polycyclic cycloalkyl groups are those defined by the respective related compounds in pp. 87873 S, pages 1 1 and 12, wherein the formula (1)-(46) must be added with a bond to form a ruthenium reactive group. Oh, this is customary for those who are accustomed to this skill. In general, a cycloaliphatic ring can form a repeating structural unit. (Please read the note on the back to write this page) ia. --Line · Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing line 1 Ding You 4, or I, C I base 2 base and 6 ene, ene Cethyl octyl, not I, olefinic I bond poly-glycol 7 double or C propyl or 1 , ene 3 yl mono-monomethylene or 00, hexyl ketone yl I I propyl butyl 5 has a 2 olefin I, with a reverse C of 1 yl group such as a sub, olefin. The base of the stilbene 2, propyl pentene ring 1 susceptor 1 00 C decenyl 3 or 〇I 4, A ke containing C 2 1 C 4 C or II, alkene C 2 1 base is C, and the paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7

Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperatives. V. Description of Invention (A) — C6 cycloalkenyl, or Cs-C8 cycloalkenyl. Examples are cyclobutenyl, cyclopentenyl, cyclohexenyl or cyclooctenyl, especially cyclopentenyl and cyclohexenyl, preferably cyclohexenyl. The C6-Ci 2 bicycloalkenyl represents a bicycloalkenyl group which may have one or more double bonds, and wherein the double bond may be on the same ring, but may also be on two rings. If there are multiple double bonds in the bicyclic structure, these biguanides may be conjugated or non-conjugated, preferably these double bonds are conjugated. Examples are bicyclo [4 · 2 ♦ 4] 12-1,7-diene-5-yl, bicyclo[4 · 2 ·4] 12- 3 -ene-5-yl, bicyclo [4 ♦ 2·4 】 12-12, a dilute, a 6-yl group, a bicyclo [4·2·3] 壬-3-alkenyl-5-yl, a bicyclo[4 · 2,3] fluorene- a 4- ene- 6-yl group, a bicyclic ring 4·2·3] 壬-7-ene-8-yl, bicyclo [4' 2 ♦ 3] 壬 -8- ene- 7-yl, wherein the numerical numbers of these examples are as follows:

C2 - Ci 2 alkylene is linear or branched, such as C2 - C8 -, C2 - C6 - or C2 - C4 monoalkylene. Examples are ethylene, propylene, butyl, pentylene, hexene, hexamethylene, sulphide, yttrium, yttrium, and undecane. Preferably, Ci-(8-alkylene*, especially Ci-C6-alkylene, preferably Ci-C4-alkylene, like methyl or butyl-1 6 - is applicable to China National Standard (CNS) A4. Specifications (210 X 297 mm) Please read the notes on the back first.

1295281 A7 B7 V. Description of invention () Support. Thus, a C2-ci2 alkylene disulfide plug is an alkylene group as defined above which bears a sulfonyl group on two fluorenyl fluorene atoms. An example is a S〇2 — ( C Η 2 C Η 2 ) z — SOz —, where z is 1–6, such as: a S〇2 - CH2 CHz - S〇2 -, or -SOz - CH (CHs) CH2-S〇2-phenylene disulfonyl, diphenylene disulfonyl and oxydiphenyl sulfonyl groups also have a sulfonyl group on the fluorenyl fluorene atom. Therefore, the result structure is: . Wonderful (please read the note on the back first to write this page)

Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperatives Substituted phenyl groups carry from one to five, for example, one, two or three, especially one or two substituents, on the phenyl ring. Substitution is preferably in the 4, 3, 4, 3, 5 - or 3, 4, 5 - position of the phenyl ring. The substituent Ci-C8 alkyl group on the Ci-C8 group is intended to mean linear or quinone-containing, and has the meaning as defined in the preceding paragraph. The definition of the substituent C3-C3 fluorencycloalkyl in the C3-C3 fluorenylalkylsulfonyl group is as defined above. -17- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281

A7 B7 V. INSTRUCTIONS (/ψ) When the reactive naphthyl, phenanthryl, heteroaryl and fluorenyl groups are substituted via one or more substituents, examples thereof are from one to five, such as single, two. Replaced by one or three, especially one or two. When Ri is a phenyl group substituted via 0R4, NR5Re and/or SR7, these 0R4, NRsR6 and SR7 substituents via the R4, Rs, R6 or R7 reactive group and other substituents on the phenyl ring' or the ring The above one carbon atom forms a 5- or 6-membered ring, for example, the following structural unit is obtained: χτ, ςσ, in the present invention, the term "doped aryl" refers to an unsubstituted or substituted reaction. Base, 3 - thiophene, 2 - sleeping,

RsReN wherein R5 and Re are as defined above, thiophene, isobenzofuranyl, oxonium, phenoxazinyl, seven V or heart 18 This paper scale applies to the Chinese National Standard (CNS) A4 specification ( 210 X 297 publicity) Please read the notes on the back first.

f Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1295281 A7 B7 V. Description of the invention (where Y is S, 0 or NR4, and R4 is as defined above. Examples are pyrazolyl, thiazolyl, oxazolyl, Isothiazolyl or isoxazolyl. Also included, for example, furanylmethyl, pyrrolyl, 1,2,4-triazolyl,

N-N

I or a 5-membered ring heterocyclic group having a fused aromatic group, such as benzimidazolyl, phenylthiol, benzofuranyl, benzoxazolyl and benzothiazolyl. Examples of other doped aryl hydrazines are pyridyl groups, especially 3-pyridyl groups.

A -------------- Pack --- (Please read the note on the back H to write this page) ^_ where R4 is as defined above, pyrimidinyl, pyrazinyl 3 * 5 Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperative, printing

Triazinyl, 2,4, 2' 2 - or 2 ' 3 -diazinyl c c | pyrazinyl, isodecyl, fluorenyl, carbazolyl, fluorenyl, isoquinoline Base, quinacridyl, phenoxazinyl or phenazinyl. In the present invention, the "heteroaryl fluorene also includes a thiol oxy group, an oxonium group's°t〇CX, [ran^〇CC

Where m is 0 or 1, R

R -19- -- line ·

Rs is as defined above. This paper size applies to the Chinese National Standard (CNS) A4 specification (210 x 297 public) 1295281 A7 B7 V. Invention description (/έ)

Or 憩锟基. Each of the heteroatoms may have a substituent as described above or as in the first item of the patent application. Camphor base, 10 - camphor base is camphor 10-base, also known as h3c CH,

Examples of the h2c C2 - C6 alkano group are an ethyl group, a propyl group, and a butyl group. An example of a group is a methoxy group having more than 2 or hexyl groups in the alkoxy group, especially B C i - C 4 alkoxy and butoxy; wherein it may also be branched. C i - C 4 alkyl and butyl sulfide, which may also be branched herein. C 2 - C β alkoxy C ( 0 )-, of which C is the number. An example is an alkyl group of a methoxyoxycarbonyl group or a pentyloxycarbonyl carbon atom which may also be a C 1 - C 1 0 tooth (please read the back note on the front page) 装· _ line · Ministry of Economic Affairs Intellectual Property Office staff The consumer cooperative prints an ethoxy group, an example of an alkylthio group of a propoxy carbon atom, a methyl sulfide, and an alkylthio group having more than 2 groups of a carbonyl group (Ci-C i - C s alkyl group is as above ethyl thio , propyl thiol carbon atom alkyl 5 alkyl) - 0 - defines a suitable carbon atom propoxycarbonyl group, with more than 2

a carbonyl group, an ethoxycarbonyl group, a group in which the alkoxy group contains a branch. Alkyl and C i -c 4 halogenated alkyl is C -20- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 ______Β7___ V. Description of invention (1) One Ci 〇— Examples of the Ci-C4 alkyl group, which are mono- or poly-substituted by halogen, Ci-Ci 〇- and Ci-1,4-alkyl group are as defined above. For example, there are from one to three, or one or two halogen atom substituents on the alkyl thiol group. Examples are methyl chloride, methyl chloride, methyl trifluoride, or 2-bromopropyl, especially methyl trifluoride or methyl trichloride. More preferred is C^-C i fluorinated alkyl. The C 2 - C 6 dentate sulfonic acid group is (c 1 - C 5 dentate alkyl) - C ( 0 ) one, wherein the Ci - C5 halogenated alkyl group is a suitable carbon atom as defined above. Examples are ethyl chloroformate, triethylammonium chloride, ruthenium trifluoride, propyl fluorenyl fluoride, fluorinated fluorenyl, or 2-propyl bromide, especially trifluoroacetate. Mercapto or triethyl sulfonate. The halogenated benzinyl group is a mono- or poly-substituted benzamidine group via a halogen and/or a Ci-C4 halogenated alkyl group, wherein the Ci-C4 halogenated alkyl group is as described above. Examples are phenanthryl pentafluoride, benzamidine trichloride, methyl benzhydryl trifluoride, especially pentafluorobenzylidene. Halogen is fluorine, chlorine, bromine or iodine, especially chlorine or fluorine, preferably fluorine 0 ------------ - (Please read the back note before writing this page) -- Line. Ministry of Economic Affairs Intellectual Property Bureau employees consumption cooperatives printed 1 base is C C. I-based phenyl benzyl benzyl diphenyl I is oxygen 3

Ethyl, ethyl benzyl phenyl I 2 2 , I group α benzyl , benzyl or benzyl group

This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (if) When Rs and Rs start and bond When the nitrogen atom forms a 5- to 6- or 7-membered ring, it can be interrupted by a 〇- or a NR4. An example is the structural formula obtained as follows: i 8 alkanesulfonyl group, a detailed description of C 1 -C 3 burning base, please read the notes on the back first

Page or Π C 醯, meaning as a sulfonyl group, 憩 醯, C 6 will be cracked and then increased (in the formula I

A C-brain group is detailed (one S 0 2 - sulfonyl 0 R 3 -C 1 sulfonium sulfonate, C 1 reactive brain base and ). Examples of the sulfonyl group and the phenanthrene are C 2 having a 0-c solution, and the addition of the formula I b, I solubility group, benzene-C 1 group C i C 1 - therefore, the group means - C 1 C 1 0 a cis-halogenated alkyl sulfonyl-C i 8 alkylhaloalkyl fluorenyl group, the phenyl group is bonded to the naphthyl sulfonate, and the corresponding reactive group is bonded to the sulfonate 8 C4 ~ C 1 2 - CI 0 phenylsulfonyl C 4 a bond or a 0 - S i - bond

The substituent for Ri is an acid cleavable group, 11 or III or lb or I lb and 111b will be described below. This effect is described, for example, in U S 4 -22-C 4 sulfonium. The group base, its I b or 逑) at 8 8 3 in acid action and acid counter I I I b alkaline imaging 7 4 0 . This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). 1295281 A7 __ B7 V. INSTRUCTION DESCRIPTION (β) Examples of suitable substituents for R i are, for example, conventional o-esters. Triyl and benzyl, tert-butyl ester of carboxylic acid, tert-butyl carbonate of phenol, sand ether of phenol, such as 0-Si(C Η 3 ) 3 , 〇II-g-c-〇一c (ch3)3, h2

—C——〇一C(CH3)3, 一〇一C一〇一C(CH3)3 or —0一C——0-R12 ; (Please read the notes on the back and fill out this page) The Intellectual Property Office employee consumption cooperative printed the two of Ri i and Ri 2 which are mutually exclusive: hydrogen, Ci-C6 alkyl, C3-C8 cycloalkyl, phenyl-Ci-C3 alkyl, or Ri 1 and Ri 2 - is Cz - Cs burnt, and Ri 3 is unsubstituted or halogen-substituted Ci -Ci decyl, unsubstituted or halogen-substituted C3 - C8 cycloalkyl, or phenyl Cl-C3 alkyl, or if Rl i and Rl 2 are not C2-C5 alkylene, then Ri 3 and Rl 2 may be C2-Cs alkyl, which may be one-zero or one-s-- The atom is interrupted. 〃 and / or 〃 or " or / and 〃 in the scope of the patent application means that there is not only one different substituent defined, but also several different substituents present together, that is, a mixture of different substituents. " At least the meaning of the word is one or more, such as one or two or three, preferably one or two. -23- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) V5J· Line · 1295281 A7 B7 V. Invention Description (^) The present invention also relates to a compound, a novel formula I b, II b or III b R'·

Rn, -R,, N"II X, (Hb), R"; hTII X, (mb), (please read the notes on the back and fill out this page)

Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Consortium: i is a phenyl group which is unsubstituted or consists of one or more Ci-Ci 2 alkyl, phenyl-Ci-C3 alkyl, Ci-C4 halogenated alkane Base, dentate 'phenyl, OR4 f NR 5 R 6 > SR 7 f SOR7 and/or SO2R7 substituted, substituents 0R4, SR7 and NRsRe are selectively via R4, Rs, R6 and/or R7 and Other substituents on the phenyl ring, or a carbon atom on the phenyl ring form a 5- or 6-membered ring; or R 〃 i is a naphthyl group, an anthracenyl group or a phenanthryl group, each of which is unsubstituted Or substituted by Ci-C6 alkyl, phenyl, 0R4 » NR 5 Re , SR7 , S0R7 and/or S02 R7, the substituents OR4, SR7 and NR5 R6 are selectively via R4, R5, Rs and /or R7 and other substituents on the Tecaki, fluorenyl or phenanthryl ring, or a carbon atom on the naphthyl, anthracenyl or phenanthryl ring form a 5 - 24 - this paper scale applies to Chinese national standards (CNS) A4 size (210 X 297 mm) A7 1295281 ___Β7___ V. Description of invention (>1) or 6-兀 ring; or R " i is a heteroaryl group, which is Substituted, or substituted by C i -C 6 alkyl, phenyl, OR4 · NR 5 Re , SR7 , S0R7 and / or s 〇 2 R7, the substituent 〇R4 'SR? and NRs Rs can be selected Reducing a 5- or 6-fluorene ring via R4, Rs, Re and/or other substituents on the heteroaryl group, or a carbon atom on the heteroaryl group; R々"i is phenylene, Naphthalene, (please read the notes on the back 3 write this page) "

Diphenylene or oxydiphenyl, wherein the substituents are unsubstituted or substituted by C i - C i 2 alkyl; or R " 〃 i is a line

The Ministry of Economic Affairs, Intellectual Property Bureau, and the Consumer Cooperatives Printing A is a 0 -, a S -, - NR4 -, a 0 (C 0 ) one, an S (CO) -, a NR4 (C0) -, a SO -, One SO2 - or one OSO2

Ai is (: 1 -Ci 2 alkylene or C2 - Ci 2 alkylene, which is made up of a -2 5 - this paper scale applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) A7 1295281 ____B7__ V. DESCRIPTION OF THE INVENTION (〆) One or more 0-interrupted; R々3 is Ci-Ci s alkylsulfonium, phenyl-Ci-C3 alkylsulfonium, camphorylsulfonyl, naphthylsulfonate, Trimethylphenylsulfonate; or phenylsulfonium hydrazide, which is substituted via one or more C 2 -Cioalkyl, Ci-C 4 alkoxy, C t -C 4 haloalkyl and/or halogen And R / 3 is phenyl disulfonate, naphthalene disulfonate, (please read the notes on the back and fill out this page)

Diphenylene is substituted by a C 1 R 4 or by phenoxycarbonyl, N R

Disulfonium, or oxydiphenylene or by C i -C i 2 2 alkylene disulfonium; hydrogen, phenyl, phenyl, anthracene, phenyloxy 5 R 6 * C disulfonate, wherein These substituents are unsubstituted by alkyl; or R / 3 is C2 alkyl, which is unsubstituted (: 1 - (: 12 alkoxy, 〇 2 - (: 12 15J- ; line - Ministry of Economics The property bureau's consumer consortium prints methyl phenyl) sulfonium or R 4 interrupted C 1 2 棊 carbonyl C 1 2 is C 2 - C and it is not alkoxy, C, phenyl sulphur, alkyl Sulfonium, phenoxycarbonyl, phenyl sulfide, phenylthiocarbonyl 2 alkyl sulfonate, phenyl sulfonium, (4 C2 - Cs alkyl fluorenyl substituted;

a C and/or a 12 alkyl group which is substituted by one or more mono- or by a phenyl group, Ο Η, C i -2- 2 Ci 2 alkoxycarbonyl, phenoxy, benzene Oxyphenylthiocarbonyl, NR5Rs-Cl-phenylsulfonate, (4-methylphenyl)sulfonate and / - 26- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 _B7_ V. Description of the invention (>)) or substituted by C2 - Cealkyl fluorenyl; or R 4 is c 2 - ci 2 alkyl fluorenyl, which is unsubstituted or derived from phenyl, OH, Ci-Ci 2 alkoxy, c2 - Ci 2 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR 5 Re , Ci-alkylsulfonate, phenylsulfonate醯, (4-methylphenyl) sulfonate and/or substituted by C 2 -C 6 alkyl fluorenyl; or R 4 is C i - C ^ 2 alkyl sulfonyl, which is unsubstituted, Or by phenyl, OH, Ci-Cl2 alkoxy, C2-ci2 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR5R6, Ci-Ci2 alkylsulfonate , phenylsulfonate, (4-methylphenyl)sulfonate and/or by- C6 alkyl fluorenyl substituted; or R 4 is phenyl sulfonate, or (4 methyl phenyl) sulfonium; R 5 and R s are each independently unrelated to hydrogen, or C ^ -C i 2 alkyl , which is unsubstituted, or consists of OH,Ci(:4 alkoxy, C2-C i 2 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, Phenylamino, phenylaminocarbonyl, Ci-Ci 2 alkylsulfonyl, phenylsulfonyl, (4-methyl-phenyl)sulfonate and/or (1-1-C6 alkylthio substituted ; or ί? 5 and R6 are C2 - Ci 2 alkyl groups * which are interrupted by one or more than one - and are unsubstituted or OH, Ci - C4 alkoxy, C2—Ci-2-alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, phenylamino, phenylaminocarbonyl, C!-Ci2 alkylsulfonyl, benzene Base sulfonate, (4-methyl-phenyl-7-- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -------------% (please first Read the notes on the back and fill out this page) Order---------Line· Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperation Printed 1292281 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperative Printed 5, Invention Description (4) Base) Sulfonamide and / or Ci - C6 alkyl fluorenyl substituted; or R5 and R6 are C2 - Ci 2 alkyl fluorenyl , which is unsubstituted, or phenyl 'OH'Ci-Ci2 alkoxy 'Cz — Ci 2 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio 'phenylthiocarbonyl, benzene Amino group, phenylamino group - 'Ci-Ci 2 alkyl group cyano, phenyl sulfonate, (4 methyl monophenyl) sulfonate and / or c2 - C6 alkyl fluorenyl substituted; or Rs and R6 are Ci—Ci 2 alkylsulfonyl, which is unsubstituted or derived from phenyl, OH, Ci-Ci 2 decyloxy, C 2 —C 2 alkoxycarbonyl, phenoxy, benzene Oxycarbonyl, phenyl thio, phenylthiocarbonyl, phenylamino, phenylaminocarbonyl, Ci-Ci 2 alkylsulfonyl, phenylsulfonyl, (4-methyl-phenyl)sulfonate And/or C2 one (: 6 alkylalkyl substituted; or R5 and Rs are phenylsulfonyl, (4-methylphenyl)sulfonate; or R5 and R6 are phenyl, benzamidine, naphthyl Sulfonamide, mercaptosulfonate or phenanthrylsulfonate; or Rs Re- and the nitrogen atom to which it is bonded form a 5-, 6- or 7-membered ring which is optionally interrupted by a 0- or by a NR4; R7 is hydrogen, phenyl, Ci —Ci 2 alkyl, which is unsubstituted or derived from phenyl, OH, Ci alkoxy, Cz-alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenyl sulfide, phenylthio Carbonyl • NR 5 R 6 , Ci-Ci2 alkyl sulfonium, phenyl sulfonium* (4 -28- (Please read the note on the back - write this page) Pack 13 · This paper scale applies to Chinese national standards (CNS ) A4 size (210 X 297 mm) 1295281 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed a monomethyl phenyl sulfonate and / or Cz - C6 alkyl fluorenyl substituted; or R7 is (: 2 a Cl 2 alkyl group interrupted by one or more mono- and which is unsubstituted or derived from phenyl, hydrazine, C i -Ci 2 alkoxy, C 2 - Ci 2 alkane Oxycarbonyl, phenoxy, phenoxy, phenyl thio, phenylthiocarbonyl, NR5R6, Ci-C 12 alkyl sulfonium, phenyl sulfonium, (4-methyl-phenyl) sulfonate醯 and / or Cz C6 alkyl fluorenyl substituted; or 1^7 is C2 - C i 2 calcined aryl 'which is unsubstituted, or by phenyl, 01^, (: 1 a (: 12 alkoxy, (: 2) —(: 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylsulfide, phenylthiocarbonyl, NRsRe/Ci-C12 alkylsulfonyl, phenylsulfonyl, (4-methyl-benzene) Substituted with sulfonate and/or C2-C6 alkyl fluorenyl; or R7 is Ci-Ci 2 alkylsulfonyl, which is unsubstituted or derived from phenyl, hydrazine H, Ci-Ci2 alkoxy , C2 — Ci2 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylsulfide, phenylthiocarbonyl, NR 5 R 6 , Ci-Ci 2 alkylsulfonate, phenylsulfonate, (4 Methyl-phenyl)sulfonate and/or C2—C6 fluorenyl substituted; or R7 is phenylsulfonyl or (4-methylphenyl)sulfonyl; provided that R 〃 i is 4 R" 3 is not methanesulfonate. Monomethylphenyl or 4-octylphenyl. Anthraquinone derivatives (or I, I b, II, II b , III and III b) can generally be prepared by methods described in the literature, for example by a suitable formula X or XI (R3 and R' 3 = H) 和所-29- (Please read the notes on the back and fill out this page) .3⁄4 订· i line. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 Description of the Invention (> fc Formula XV, XVI or XV II acid halide (e.g., sulfonic acid) (e.g., R 3 C 1 or C 1 -R ' 3 - C 1 ) is reacted.

—Η ΝII 丨\ XX

R3ci or R%CI (X) (XV) (XVI) or

Rr

NII X\c/R2 eight XX α-fv-ci

H (xi) (XVII) -------------- Pack - (Please read the note on the back first to write this page)

Rr

/0—R3 NII x, c/R2 eight XX N"II,c, •R,3

Rr

, c, eight XX (III) _ line · Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed in which Ri, Rz, R3, R, 3 and x are as defined above. These reactions can be carried out in an inert solvent such as toluene 'tetrahydrofuran (THF) or dimethylformamide (DMF), and the reaction is carried out in the presence of a base such as a tertiary amine such as triethyl The amine * or this reaction can also be carried out by the salt of hydrazine and the chloride of the desired acid. These reaction methods are described, for example, in EP-486 15 . The sodium salt of hydrazine can be prepared, for example, by the reaction of hydrazine and sodium amide in dimethylformamide. These reactions are in this field - 30 - this paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) A7 1295281 _ ___ B7_ V. The invention description () is well known and generally available in The temperature range is from 15 to +503⁄4, preferably from 〇 to 2 ο. The starting materials can be prepared by various methods* as described in standard chemical reference books (eg J. March, Advanced Organic Chemistry, 4th Edition, Wiley)

Intersceience, 1992) or in specific articles such as S. R. Sandler & W. Karo, Organic Functional Group Preparation, Vol. 3, Academic Press. One of the most convenient methods is, for example, the reaction of hydrazine with a hydroxylamine or a salt thereof in a polar solvent such as an aqueous solution of ethylene or ethanol. In this case, a base such as sodium acetate can be added to the p Η value of the reaction mixture, and the reaction rate and p H value of the reaction are known. The base can be added at the beginning of the reaction, or During the reaction period, the performance was added. Alkaline solvents, like pyridine, can also be used as bases and/or solvents or co-solvents. The reaction temperature is generally the reflux temperature of the mixture, usually about 60 to 120 °C. Another convenient method for synthesizing hydrazine is the nitration of the hydrazone active benzyl group of K nitrous acid or alkyl nitrite. Alkaline environment, as described in Organic Syntheses coll. Vol. VI (J. Wiley & Sons, New York, 1 988), PP 199 and 840, and acidic environments, as described in Organic Synthesis coll. vol V· pp32 And 373, coll·vol. III, ppl91 and 513, coll. vol. II, pp. 2 0 2 , 2 0 4 and 363, all suitable for the preparation of hydrazine as a starting material for the compounds of the invention. Nitrous acid is usually produced by sodium nitrite, and the alkyl nitrite can be, for example, methyl nitrite-3. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). (Please read the back first. Note on this page again) 3⁄4

Order ---------Line II Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperative Printed 1295281 A7 B7 V. Invention Description (d) Acid ester, ethyl nitrite, isopropyl nitrite, butyl Nitrite, isoamyl nitrite. The synthetic method can produce the compound of formula I, II and III* or the isomer of the compound of formula lb, I lb and II lb, the bismuth of the oxime, K cis (cix, Z) and trans (trans, E) is present in the form or in the presence of a mixture of the two geometric isomers. In the present invention, these two geometric isomers and any mixture of the two isomers can be used. Accordingly, the invention also relates to compounds of formula I, I I and I I I, or mixtures of the compound isomers of formulas lb * I lb and I I lb . Although the individual geometric isomers of the compounds of formulas I, 11 and III, or the compounds of formulae Ib, IIb and III b (Z and E versions) and any mixtures of these two geometric isomers may be used, however, It has been found that compounds of formula I, II and III in a particular configuration, or compounds of formulas lb, I lb and II lb (Z-configuration) have better thermal stability than compounds of other configurations (E-configuration). Thus, preferably, the compounds of the invention are thermally stable isomers (Z-configuration) using a single formula I, I I and I I I or lb, I lb and II lb. The synthesis as a starting material oxime produces a mixture of isomers. Surprisingly, it has been found that a mixture of isomers used as a starting material can be converted to a single isomer by decanoic treatment. type). Using these single-configuration isomers (Ζ-configuration) as starting materials, compounds of formula I, II and IΪI, or formulas Ib, IIb, and III b compound. Therefore, the present invention also applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) for a -32- paper scale ----------I---installation - (please read first Notes on the back of this page) tSJ· -- Line _ Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1295281 Α7 Β7 V. Invention Description (>1) Synthesis of Formulas I, II and III with Higher Thermal Stability A method of hydrating a compound, or a compound of I b , II b and III b, comprising: 1) a citric acid treatment, converting a relative isomer mixture of hydrazine into a single isomer form, and 2) m-heterogeneous The formula is reacted with the desired acid halide. Thus, one of the subject matter of the present invention is a thermally stable Formula I, II and III oxime ester compound as claimed in claim 1 or lb, I lb and II lb 如 as claimed in claim 10 Specific methods for the isomer of an ester compound, comprising: (1) a mixture of isomers of a free oxime compound of the formula X or XI obtained by a conventional method of K acid treatment, -------------- Loading --- (Please read the note on the back to write this page), 0- Η

/0—Η /II /C\c/B2 (X) l\ XX N"II X,

C VIII (XI), - Line · Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, printed in which Ri, R2 and X are as defined above, and (2) prepared single isomers and relatives XV, XV I or XV II acid halide reaction, R 3 C 1 (XV) -33- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) A7 B7 Ministry of Economic Affairs Intellectual Property Office staff consumption Co-operative printing! 295281 V. Inventive Note (y) R 〃 3 C 1 (XVI) C 1 - R,3 - C 1 (XVII), wherein R3 and R/3 are as defined above, and R〃 3 is as follows As defined, the reaction of converting the oxime isomer mixture into the desired single isomer form is usually carried out in an inert solvent such as methyl chloride, ethyl acetate, toluene, tetrahydrofuran or dimethylformamidine. Amine* and the reaction is in the presence of an acid such as hydrochloric acid, sulfuric acid, acetic acid, trifluoroacetic acid or trifluoromethanesulfonic acid. This reaction is usually carried out at temperatures ranging from 1 527 to + 1 203⁄4, preferably from 0 ° C to 8 Torr, more preferably from 5 £ 0 to 40 Torr. This compound can be isolated by methods known in the art, such as distillation, crystallization, and chromatography. An example of a conventional method for preparing a compound of the formula X or XI oxime as a starting material is as described above. Advantageous compounds are compounds of the formulae I b , II b and III b , wherein: R! is hydrogen, unsubstituted C 2 -C 12 alkyl; Ci alkyl, which is substituted by C 3 -C 3 fluorencycloalkyl; Ri is C2_Ci 2 alkenyl, C 4 -C 8 cycloalkenyl, C 6 -C i 2bicycloalkenyl, or camphoryl, ' or Ri is phenyl, which is composed of one or more Ci 〇 - Ci 2 alkyl, haloalkyl, chloro, 0R4, NR5R6, SR7 and/or a S-phenyl substituted wherein the OR 4 , SR7 and NRs Re substituents are selectively via the reactive group R4, Rs, -34 - This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page)

!295281 A7 B7 V. Invention Description (Correct) -------------1 Pack - (Please read the note on the back first to write this page)

Re and / or R7 and other substituents on the benzene ring, or a carbon atom on the benzene ring to form a 5- or 6-membered ring or Ri is 2-naphthyl, anthracenyl or phenanthryl, of which 2 —naphthyl, anthracenyl and phenanthryl are unsubstituted or substituted by C i -C 6 alkyl, phenyl, 0 R 4 ^ NR 5 R 6 , SR7 and/or an S-phenyl group. The 0R4, SR7 and NRs R6 substituents are optionally via the reactive groups R4*R5, R6 and/or R7 and other substituents on the naphthyl, anthracenyl or phenanthryl ring, or with naphthyl, fluorenyl or A carbon atom on the phenanthryl ring forms a 5- or 6-membered ring; the line or 1^^ is a heteroaryl group which is unsubstituted or consists of a Ci-Ce alkyl group, a phenyl group, 0R4, NRsR6, SR7 and/or an S-phenyl substituted wherein the ORR, SR7 and NRs Rs substituents are optionally via a reactive group R4, Rs, R6 and/or R7 and other substituents on the heteroaryl ring, or And a carbon atom on the heteroaryl ring forms a 5- or 6-membered ring; the Ministry of Economic Intelligence's Intellectual Property Bureau employee consumption cooperative prints all of the Ri substituents (except hydrogen K), which may additionally contain one in the acid under Will cleave one of the 0-C-bonds or a 0-S i-group substituted; R4 is phenyl, - Ci 2 alkyl, which is unsubstituted, or phenyl, OH, Ci Cl 2 alkyl, Ci—Ci 2 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonate and/or substituted by C 2 -Cs alkyl fluorenyl; or R 4 is C 2 -Cl 2 Alkyl group, which is interrupted by one or more zeros, and which is unsubstituted* or by benzene-35- this paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 public) 1295281 A7 B7 V. Description of the invention (θ) group, OH, Cv — Ci 2 alkoxy, Ci — Cl 2 alkyl sulfonium phenyl sulfonate, (4-methyl benzoquinone) sulfonate and/or by C 2 — C6 alkylalkyl substituted; R7 is C2 - Ci 2 alkyl which is unsubstituted or substituted by 0H and / or C i - C 4 alkoxy; or R7 is C2 - Ci 2 alkyl, It is interrupted by one or more hydrazines and is unsubstituted or substituted by 0H and/or Ci-C4 alkoxy; and all other substituents are as described above. Other advantageous compounds of formula lb, I lb and II lb are: wherein: R 3 is C 2 -C 8 alkylsulfonyl, Ci -Ci 〇haloalkylsulfonyl, camphorylsulfonyl, phenyl-Ci a C3 alkylsulfonyl group, a C3 - Ci 2 cycloalkylsulfonyl group, a naphthylsulfonyl group, a decylsulfonyl group, or a phenanthrylsulfonyl group, wherein the substituent C3 - Ci 2 cycloalkylsulfonate Base, phenyl-C i -C3 alkylsulfonyl, phenylsulfonyl, naphthylsulfonyl, fluorenylsulfonyl and phenanthrylsulfonyl cycloalkyl, naphthyl, anthracenyl and phenanthrene The base is unsubstituted or consists of one or more halogens, Ci-C4 halogenated alkyl (please read the phonetic on the back? Please fill out this page) - Line · Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative print

4 C ; Halo 1 and C ο 4 C "I ί C , 2 1 I take a base ο C base e 1 benzene S , burn R c , ο S 4 5 » S 7 phenyl CR alkane R , IN halogen 6 , base i 1 17 alkane C or more c R 5 , \ or 1 ο . 1 7 and a CsJ ο 3c RI a CC* I o N by , , 1 ο ο via 2 4 cc S is o R , , ο其Ν ο 2 4 7 , , , o RR base N sulfur No, benzene C group, , I is, burned N sulfur ο 3 base 4 C based IR alkane C, alkane} or I This paper scale applies to Chinese national standards (CNS) A4 specification (210 X 297 mm) Ϊ295281 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing

5. Description of the invention (young) / or a NRsRs substituted; or R 3 is a phenyl group via one or more dentates, ci-C 4 halogenated alkyl, CN, N〇2, C2-alkyl, Phenyl, Ci~C4 alkyl sulphur, OR4 'COOR7, R7〇S〇2 - and/or a NR5 R5 substituted; or 尺3 is a C2 - C6 halogenated fluorenyl group, or a halogenated benzamidine group; * is phenyl, Ci-Ci 2 alkyl, which is unsubstituted or via phenylhydrazine, OH, C i -Ci 2 alkoxy, Ci-Ci 2 alkylsulfonyl, phenylsulfonyl, (4-tolylphenyl)sulfonyl and/or substituted by c 2 —c 6 alkylalkyl; or the rule 4 is C 2 —C 2 alkyl, interrupted by one or more — 0 — And it is unsubstituted or consists of phenyl, OH, Ci-Ci 2 alkoxy, Ci-Ci2 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl and / Or substituted by a C2-C6 alkyl fluorenyl group; and all other substituents are as defined above. Particularly advantageous compounds of the formula I, I b, II, II b, III, III b are: wherein R i is phenyl which is unsubstituted or consists of one or more substituents C i —Cl 2 alkyl, benzene Substituted by a Ci-C3 alkyl group, a halogen, OR4, NR 5 Re , SR7 , SOR7 and/or SO2 R7 wherein the substituent OR4 selectively forms a 6-membered ring via the R4 reactive group; or R i is naphthalene Base or thizone; R 'i is -37- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 metric H (please read the back note before writing this page) Binding._ 丨线· 1295281 A7 B7 V. Description of invention (shake)

Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A is a 0-, or a S-; Αι is Ci-Ci 2 burnt; R2 is halogen or Ci-Ci 〇 halogenated alkyl; R3 is Ci-Ci 8 alkyl Sulfhydryl, camphorylsulfonyl, phenyl-Ci-C3 alkylsulfonium, phenylsulfonyl, naphthylsulfonium, wherein the phenyl group on the phenylsulfonium is unsubstituted, or by Ci - Ci 6 alkyl, or 0 R 4 substituted; R / 3 is phenyl disulfonium; X is fluorine; R 4 is phenyl, Ci -Ci 8 alkyl, which is unsubstituted or C 2 - C i 2 alkoxycarbonyl substituted; or R 4 is C 2 —C 8 alkyl, which is interrupted by one or more —O— and is substituted by phenyl; Rs and Re are Cl—Ci 8 Sulfhydryl; R7 is phenyl, or Cr-Ci8 alkyl. Preferred compounds of formula I, I b , II , II b , III and 1 II b are those wherein: R t is phenyl which is unsubstituted or consists of one or more substituents C i - C! 2 alkane Base, halogen * 0R4 or SR7 replaced; -3 8 - --------------- Pack--- (Please read the note on the back JII to write this page) • Line paper The scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). The Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative prints that R 2 is fluorine or C 1 -C 6 fluorinated alkyl; R 3 is C 1 -C 1 2 alkyl sulfonate m camphor - 1 〇 - sulfonyl quinone # naphthyl sulfonium 9 phenyl sulfonate wherein the phenyl group of this group is unsubstituted or consists of one or more C 1 - C 1 6 alkyl groups or 〇R 4 substituted by $ X is fluorine t R 4 is C 1 — C 4 alkyl 1 R 7 is C 1 —C 4 alkyl 1 i ) if R 1 is phenyl 4 monomethylphenyl $ (methyl Sulfur) Phenyl 9 and R 2 and X are both fluorine and R 3 is not 4-methylphenylsulfonyl 1 i 1) Suppose R 1 is 4-methylphenyl or 4-octylphenyl and RZ and X are both fluorine 9 then R 3 is not 4 monomethylsulfonyl 1 1 1 1 ) If R 1 is benzene Base % 4 - methylphenyl 4 -methoxyphenyl 4 - phenyl chloride chlorotrifluoromethyl or cyclohexyl 5 and R 2 and X are both fluorine and R 3 is not phenylsulfonyl $ ( V 1 ) If R 1 is phenyl 9 and R 2 is a pentafluorinated ethyl group and X is a fluorine f, then R 3 is not a phenylsulfonyl group. Particularly preferred is 2, 2, 2 - trifluoro-1. —Phenyl-Ethyl Ketone 肟-〇Methanesulfonate 1 2 > 2 > 2 Trifluoro-1 - Phenyl Ethyl Ketone Oxime - (1 0-Mentylsulfonate) > 2 > 2 赘2 - trifluoro- 1 phenyl acetophenone ( 4 -methoxyphenyl sulfonate) f 2 2 2 - difluoro- 1 - ethyl ketone oxime - 〇一 ( 1 monom sulfonate) t 2 2 9 2 —trifluoro- 1 -phenyl- Ethyl ketone oxime - 〇 - (2 - naphthyl sulfonate) 1 2 2 9 2 trifluoro - 1 - phenyl monoethyl ketone oxime - 〇一 (2 - 39 - 1295281 A7 ^ _ B7 V, invention Note (X) This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page)

1295281 A7 B7 V. Description of the invention (Η) 4,6-trimethylphenyl sulfonate); 2,2,2-trifluoro- 1 ketone oxime- 0 - '(1 0 - camphoryl sulfonic acid one ( 4 monomethylphenyl)ethyl ester); 2,2,2-trifluoro 1 -( 4 -methylphenyl) ethyl hydrazine - 0 - (methyl sulfonate); 2, 2, 2 - Trifluoro-1(2-methylphenyl)-ethanone oxime-0-(10-2,2,2-trifluoro-l-(2,4-12-100-(10-camphoryl sulfonate) Acid ester 4 dimethyl phenyl sulfhydryl sulfonate); methyl phenyl) monoethyl hydrazine); 2, 2, 2 - trifluoro-please first read the back of the precautions

One (2 sulfonate); 2,2,2-yl)-ethanone oxime-0-(2trifluoro-l-(1,4,6(1 0-decyl sulfonate))-B Copper ruthenium-O-(1-naphthyltrifluoro-l-(2,4-dimethylphenyl-naphthalenyl-trimethylsulfonate phenyl)-ethanone ketone oxime--trifluoro- 6-three Methylphenyl)-ethanone oxime-0-(1 -4,6-ester); 2,2,2-trifluoro-l-one ketone-0-(2-naphthyl)-ethylene trifluoride 1 ester; 2, (2, sulfonate 1 - (2 - naphthylsulfonic acid trimethylbenzene t - (4-methoxyphenyl) 2,2 - trifluoro-1 - (e-ketone oxime - 0 -Methylsulfonic acid 4-methylthiophenyl)-B-Ministry of Commerce, Intellectual Property Bureau, Staff Consumption Cooperative, printing ketone oxime, 0-methanesulfonate; 2,2,2-trifluoro-1 4 A, 3,3 (10-yl)-ethyl-(phenyloxyphenyl)-ethyl hydrazine, 4,4,4 a t: fluoro-indenyl sulfonate); 2 * ketone 8 bow Ethyl hydrazine (3 0-methanesulfonate; 2,2 1 -benzene 2 , 2 -butanone oxime- 0-trifluoro-monomethanesulfonate; 2 肟一〇1 (Benzene trifluoride-1-10-is camphoryl sulfonate; 2,2 -40- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 Ministry of Economics intellectual property Bureau employee consumption cooperative printed B7_5, invention description (β), 2-trifluoro-l-(phenyl)-ethanone ketone- 0-(4-methoxyphenyl) sulfonate; 2,2 , 2 -trifluoro- 1 -(phenyl)-ethyl fluorene bow 0 - (1 - hexyl) phthalate; 2,2,2 -trifluoro- 1 -(phenyl)-ethanone oxime 0 - ( 2 - Cai Ke) sulfonate; 2,2, 2 -trifluoro-1(phenyl)-ethanone oxime-0-(2,4,6-trimethylphenyl)sulfonate ; 2,2,2 -trifluoro-l-(4-methylphenyl)-ethanone oxime-0-(10-camphoryl) sulfonate; 2, 2,2-trifluoro- 1 (4 Monomethylphenyl)-ethanone oxime- 0-methanesulfonate; 2,2,2-trifluoro-l-(2-methylphenyl)-ethanone oxime- 0 - (10 - camphoryl Sulfonic acid ester; 2,2,2-trifluoro-1(2,4-dimethylphenyl)-B肟0—(1-naphthyl)sulfonate; 2,2,2-trifluoro-1(2,4-dimethylphenyl)-ethanone oxime-0-(2-naphthyl)sulfonate Acid ester; 2,2,2-trifluoro-1(2,4,6-trimethylphenyl)-ethanone oxime-one (10-camphoryl) sulfonate; 2,2,2 — Trifluoro-1(2,4,6-trimethylphenyl)-ethanone oxime-0-(1-naphthyl)sulfonate; 2,2,2-trifluoro-1 (2,4) ,6-trimethylphenyl)ethanone oxime- 0-(2-naphthyl)sulfonate; 2,2,2-trifluoro-l-(4-methoxyphenyl)-ethanone oxime 0-methanesulfonate; 2,2,2-trifluoro-l-(4-monomethylphenyl)-ethanone oxime-methyl-sulfonate; 2,2,2-trifluoro 1-1(3,4-dimethoxyphenyl)-ethanone oxime- 0-methanesulfonate; 2,2,2-trifluoro-l-(4-methoxyphenyl)-B嗣肟一0———4卜 (Please read the notes on the back and fill out this page)

Ld· - _ line · This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. Invention description (V) -------------- —— (Please read the note on the back to write this page) (4 Methylphenyl) sulfonate; 2, 2, 2 - trifluoro-1 - (4-methoxyphenyl) 1-ethanone oxime 0-(4-methoxyphenyl) sulfonate; 2,2,2-trifluoro-l-(4-methoxyphenyl)-ethoxime-(4-dodecyl) Phenyl)sulfonate; 2,2,2-trifluoro-l-(4-methoxyphenyl)-ethanone oxime-octyl sulfonate; 2,2,2-trifluoro- 1 Mono(4-monomethylphenyl)-ethanone ketone-O-(4-methoxyphenyl) sulfonate; 2,2,2-trifluoro-l-(4-monomethylbenzene) Ethyl ketone oxime 0 - (4 - dodecylphenyl) sulfonate; 2, 2, 2 - trifluoro-1 - (4-monomethylphenyl) 1-ethanone oxime - octyl sulfonate; 2,2,2-trifluoro-l-(4-monomethylphenyl)-ethanone oxime-(2-naphthyl-line-yl) sulfonate 2,2,2-trifluoro-l-(2-methylphenyl)-ethyl-deutero- 0-methylsulfonate; 2,2,2-trifluoro-l-(4-methylphenyl) Ethyl ketone oxime 0-phenyl sulfonate; 2,2,2-trifluoro-l-(4-phenylphenyl chloride)-ethanone oxime-O-phenyl sulfonate; 2,2, 3,3,4,4,4-heptafluoro-l-(phenyl)-butanone oxime- 0 (10-camphoric) sulfonate; 2,2,2 — Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative Printing trifluoro-l-naphthyl-ethanone oxime- 0-methanesulfonate; 2,2,2-trifluoro-2-n-naphthyl-e-ketoneoxime-methylsulfonate; 2,2-trifluoro-l-[4-phenylmethylphenyl]-ethanone oxime-o-methylsulfonate; 2,2,2-trifluoro-1-[4-(phenyl- 1 , 4 dioxoindol-1-yl)phenyl]monoethyl ketone oxime-methanesulfonate; 2,2,2-trifluoro- 1 -naphthyl-ethyl ketone oxime-propyl Base sulfonate-42- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm)

CH3〇2S-0-N 1295281 A7 B7 V. INSTRUCTION DESCRIPTION (V}) acid ester; 2,2,2-trifluoro-2-n-naphthyl-ethanone ketone-propyl propyl sulfonate; 2,2 , 2 -trifluoro-l-[4-phenylmethylphenyl]-ethanone oxime- 0-propyl sulfonate; 2,2,2-trifluoro-l-[4-methylsulfonylphenyl 】 1-Ethyl ketone oxime 0 - propyl sulfonate; 1, 3 - bis [1 - (4- phenoxyphenyl) - 2, 2, 2 - trifluoroacetate B bow - 0 - 醯Phenyl; "N-〇一S02CH3 C3H7〇2S—0—N .

"V/〇-(CH2)2-°\_^C, Cf3 ; f3c-CH^〇'(CH2)2'HI/ C :/N_〇 a s〇?c3h7 'cf3

(Please read the precautions on the back and then fill out this page) 2,2,2 -Trifluoro-1 -[4-methylsulfonyloxyphenyl]-ethyl-3-pyrene-propyl sulfonate; 2,2 methylcarbonyloxyphenyl] 2 trifluoro- 1 - 1 - 4 - ethyl ketone 0 - 0 - propyl vinegar; 2, 2, 2 - trifluoro-[6H, 7H - 5, 8-dioxonaphthalene-2-yl]-acetamidine B-oxo-propylate; 2,2,2-trifluoro-l-[4-methoxycarbonylmethoxy----- ----Line· Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumers Cooperative, Printing Phenyl] 1-Ethyl Ketone O-Propyl Sulfate 1-1 [4-Amino-I-Oxa-Pentyl-1 2,2-trifluoro-1-ylphenyl]-ethanone 0-o- 2,2 2 trifluoro-propyl sulfonate; 2-(methoxycarbonyl)-(4)-phenyl 】 1-Ethyl ketone oxime 0 [3,5-dimethyl-4-tetraethoxy 2,trifluoro-l-[4-phenylmethoxyphenyl]-ethanone oxime-monopropyl sulfonate ; 2,2,2 -trifluoro-l-[2-thiophenyl]-ethanone oxime-o-propyl sulfonate; and 2,2,2 - three Fluorine-1 propyl sulfonate; 2 -43 This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 Α7 Β7 V. Invention description (y) One [1 dioxo sulphur Benzene-2-yl)]ethanone- 0-propyl sulfonate. The methylsulfonyl group, the methoxy 'ethoxy group or the methylcarbonyl group can also be substituted with other sulfonylalkylsulfonyl*alkoxy or alkylcarbonyl groups. The methyl group of the alkylsulfonyl ester group can also be easily substituted by other alkyl groups. The compound of the formula I, II or III can be used as a light sensitive acid supply agent in the photoresist. The photoresist system can be imaged by a system image containing a compound of formula I' I I or I I I followed by imaging. A chemically amplified photoresist refers to a photoresist composition in which a radiation sensitive component provides a catalytic amount of an acid which in turn catalyzes a chemical reaction of at least one acid sensitive component of the photoresist surface. As a result, a difference occurs in the solubility in the unilluminated region and the photo-light region of the photoresist. Because of the catalytic nature of this process, multiple reactions can be induced from one reaction point to another as one acid molecule diffuses through the reaction polymerization parent material, as long as it is not caught or destroyed by any secondary reaction. Therefore, a very small acid concentration results in a very large difference in solubility between the exposed and unexposed regions in the photoresist, and only a very small concentration of the latent acid compound is required. As a result, a photoresist having high contrast and high transparency can be formed at the time of optical exposure at the Μ exposure wavelength, and a steep, vertical image profile of high light sensitivity can be formed. However, the result of this catalytic procedure must be that the latent acid catalyst is very chemically and thermally stable (as long as it is not illuminated), and does not prevent acid generation during storage or processing of the photoresist, in most cases. The catalyst requires a post-exposure baking step to initiate or complete a catalytic reaction that can result in a difference in solubility. Latent acid catalyst in liquid photoresist formulation and solid-44- This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the note on the back page below) ιτ Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1295281 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (w) The photoresist film must also have good solubility, to prevent any possible particle production, and This particle may affect the application of these photoresists in microelectronic manufacturing processes. Conversely, the positive-like photoresist material based on the chemical amplification mechanism must contain a high concentration of latent acid, because only the concentration of the acid generated from the latent acid during exposure can increase the exposure area in the alkaline imaging agent. Solubility in the middle. Since the low acid concentration has little effect in changing the dissolution rate of the photoresist, and here, the reaction proceeds substantially without post-exposure baking, so the chemical and thermal stability requirements for the latent acid are required to be more than the chemically amplified positive photoresist. a lot less. These photoresists also require higher exposure doses to produce sufficient acid to allow the exposure zone to achieve sufficient solubility in alkaline imaging agents, but also suffer from low optical clarity (because high concentrations of latent acid are required) ), thus producing low resolution and tilted images. Therefore, the photo-sensitivity, resolution, and resulting image of the photoresist composition produced by non-chemical amplification techniques are inferior to chemically amplified photoresists. It is clear from the above that the chemical and thermal stability of a latent acid is important for chemically amplified photoresists, and the latent acid that can be operated in non-chemically amplified photoresists does not need to be Application in chemically amplified photoresists* This is due to the requirements of different acid diffusion, acid strength and thermal and chemical stability. 0 Preferred photoresist compositions are compounds of formulas I, II and III, and Ri is phenyl. Is unsubstituted, or by Ci-C6 alkyl*benzene-45- (please read the back note before writing this page) too. · -Line · This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. Description of invention (n Printed by the Consumers' Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs

R group, 0 N R 5 is a group R, or and I I I R 3 is a phenyl group in a sulfonyl phenyl sulfonate, 憩 is an unsubstituted group, C C 4 alkane 0 0 - this I I and . This R 4 , SRR 6 substituted 4 , R 5 and 7 , a S —phenyl, halogen and/or by, substituents 0R 4 and NR 5 Rs may be selective via trans/ or R 6 and other substituents on the phenyl ring A carbon atom on the benzene ring forms a 5- or 6-membered ring. It is a favorable photoresist composition in which among the formulae I, II, and the compound, C 1 - C 1 , camphorylsulfonate m ^ 9 m μ: a C 1 -cylsulfonyl group and substituted or N , N 0 2 thiol, 0 R , R 7 0 S The preferred compound of the invention III is an 8-alkylsulfonyl fluorenyl group, a C sulfonyl fluorenyl group, a decyl 3 alkyl sulfonyl fluorenyl sulfonyl group. By one or more

, C i 4 , C 0 2 — group of chemical emissions is of formula I

—CI 0 0 R and/or large photoresist, a , I , phenyl C 1 8 sulfonyl, phenylphenyl, halogen, 6 alkyl-C 1 -C 3 alkyl halide or phenanthryl Sulfonylnaphthyl, C 1 -yl sulfonyl, sulfonyl, its naphthylsulfonyl and phenanthryl C 4 haloalkyl

Phenyl, C

Ci—C4 thiol-C-N R agent composition where X I a and

5 R 6 is a package and R 2 III substituted. Containing Formula I, both of which are fluorine a compounds,

(Please read the notes on the back first. H--- 1 Write this page) . - Line · N~0—R-II 3 J, (10), R. / CF, Π1 — N_0_R3 II -c, [CF3 J (Ha), 2 _ Ν—ΟΝ cf3 -4 6 This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) • R, 3 (Mia>, 1295281 A7 B7

V. Description of invention (c) Printed by the Consumers' Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs, where Ri, R'1, R3 and R'3 are as defined above. A particularly preferred chemically amplified photoresist composition is a composition comprising at least one compound of formula I a, wherein: R i is an unsubstituted phenyl group, or a C i -C 4 alkyl group, a C i -C 4 alkoxy group, Ci-C4 alkylthio or halogen substituted one or more phenyl groups, r3 is Ci-Ci β alkylsulfonyl, C3 - C2 anthracenylsulfonyl, phenyl-Ci-C3 alkylsulfonate , camphorylsulfonyl, naphthylsulfonyl, or phenylsulfonyl; wherein these substituents are unsubstituted or consist of Ci-Ciz alkyl, Ci-C4 alkoxy, Ci-C4 alkane a group, Cx - (: 4 alkyl sulfide, N 2 or halogen substituted. According to other preferred compositions of the invention, R i other than hydroquinone is via a bond having a 0 - C bond or a 0 - S i - a group substituted by hydrazine, which is cleaved under the action of an acid. The result of an acid-catalyzed reaction of the photoresist produced by the photoresist or after the irradiation of the light causes the solubility of the photoresist in the illuminating and unilluminated areas. The difference can be divided into two types depending on whether or not other components are present in the photoresist. If the composition of the present invention is included in the photo The photoresist is positive after adding the composition to the solubility of the composition. Therefore, the present invention relates to a chemically amplified positive photoresist. On the other hand, if the composition of the composition is illuminated, Reducing the solubility of the composition, the photoresist is negative. Therefore, the present invention also applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) for the one-47- paper scale (please read the back first) Precautions on this page) - Loading - Line · 1295281 A7 V. Invention Description (w) A chemically amplified negative photoresist. -------------- Installed - (please Read the note on the back page. A single or polymeric compound that reduces the rate of dissolution of the additional alkaline soluble binder resin in the photoresist formulation in the uncalendered zone, and is essentially in the unexposed zone. Is insoluble in alkali, such a photoresist film in an alkaline solution, can remain in the unexposed area after development, but will crack in the presence of acid ' or can be recombined, so the reaction product in the alkaline imaging agent The monomer or polymer compound is called a dissolution inhibitor. According to a particular embodiment of the invention, there is provided a chemically amplified, substantially basic, developable photoresist composition comprising: (a1) at least one polymer having an acid-unstable group, Decomposes in the presence of an acid and increases the solubility of the photoresist film in the aqueous alkaline developer solution in the unexposed areas, and (b) at least one compound of formula I, II or III. Another embodiment of the invention is A chemically amplified positively alkaline-visible photoresist composition comprising: (1) at least one carcass or oligo-polymeric dissolution inhibiting at least one acid-unstable group An agent which decomposes in the presence of an acid and which increases the solubility in an aqueous alkaline developer solution, and at least one basic-soluble polymer, and (b) at least one compound of the formula I, II or III. Another specific embodiment of the present invention is a chemically amplified, substantially alkaline, photodevelopable photoresist composition* comprising: (a1) at least one polymer having an acid labile group, the acid labier group being present in the acid It will decompose and increase the solubility in the exposed area in the alkaline developer -48~ This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau staff consumption Co-operative printing 5, invention description (γ) solution; (a 2) - steroid or oligomeric dissolution inhibitor, which has at least one acid unstable group, will decompose in the presence of acid, and increase the alkali in the exposed area Solubility; (a 3 ) - a base-soluble monomer, an oligomeric or polymeric compound at a concentration that maintains the photoresist film substantially insoluble in the alkaline developer in the unexposed areas, and (b) at least A compound of formula I, II or III. Accordingly, the present invention is also directed to a chemically amplified photoresist composition comprising: (a1) at least one polymer comprising an acid-unstable group, which decomposes in the presence of an acid and which is increased in alkalinity The solubility in the aqueous solution of the developer, and/or (a 2) at least one monomer or oligomeric dissolution inhibitor, which has an acid-unstable group, decomposes in the presence of an acid, and can increase in alkalinity a solubility in an aqueous solution of the image, and/or (a3) at least one base-soluble monomer, an oligomeric polymerized or polymerized compound; and (b) at least one compound of formula I, II or III as a light-sensitive acid supply agent . In addition to component (b), the composition additionally includes other photo-sensitive acid supply agents, and/or (c) other additives. This chemically amplified positive photoresist is traced to, for example, E. -49- -------------- loaded i — (please read the notes on the back first to write this page) Order · Line · This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 Α7 Β7 V. Invention Description (Du)

Reichmanis, FM Houlihan, 0. Nalaraasu, TX N e enan, Chein· Mater. 1991, 3, 39 4 ; or CG Willson, ^ Introduction to Microlithography, 2nd. Ed; LS Thompson, C. G. Wilson, MJ· Bowden, Eds. , Amer . C hero . S oc . , Washington DC, 1 9 9 4, ρ·139〇 decomposes into aromatic hydrazine, carboxyl, keto and aldehyde groups in the presence of acid, and increases in alkaline Suitable examples of the soluble acid-unstable group in the aqueous developer solution are alkoxyalkyl ether groups, tetrahydrofuran ether groups, tetrahydropyranyl ether groups, tert-alkyl ester groups, triyl ether groups, mercapto groups. Ether group, alkyl carbonate group, such as tert-butylcarbonyloxy-, triester, decyl, alkoxymethyl ester, decyl ester, acetal, ketal, tetrahydrogen An oxime ester group, a tetrafuranyl ester group, a tertiary alkyl ether group, a tertiary alkyl ester group* and the like. a polymer having a functional group capable of decomposing under the action of an acid, which can increase the solubility of the photoresist film containing the polymer in an alkaline developer solution, and which can be added to the positive photoresist of the present invention, The polymer may have an acid-unstable group in the backbone, and/or its side chains, preferably containing the acid-unstable group on its side. A polymer having an acid-unstable group suitable for use in the present invention may be prepared by reacting a polymer analog, converting part or all of the basic soluble group into each acid-unstable group, or directly A monomer (co)polymerization reaction with an acid-unstable group linkage is described, for example, in ΕΡ-254853, EP-878738, EP-877293, JP-A-2-25850, JP-A-3- 2 2 3 8 6 0 and JP-A- 4 - 2 5 1 2 5 9. -50- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the note on the back to write this page) Installation-Line· Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing! 295281 A7 B7 i, invention description (d) In the present invention, a polymer having an acid-stability group beside the trunk is preferably one having, for example, a mercapto ether, an acetal, a ketal, and an alkoxyalkyl ester. a polymer of a group (so-called deuterium-energy-energy-blocking block) which is completely cleaved at a relatively low post-exposure temperature (essentially between room temperature and 1 lot), or these polymers have, for example a polymer of tert-butyl ester or tert-butoxycarbonyl (TOBC) or other ester group containing a primary or tertiary carbon atom adjacent to the ester group 鐽 oxygen atom (so-called hydrazine) High-activated energy block groups), these groups require a higher baking temperature (essentially > 1 1 〇υ) M to completely deblock in the presence of acid. Mixing systems are also available in which two (high activation energy block groups and low activation energy block groups) groups are present in a polymer. Alternatively, the polymer blends of the polymers, each utilizing a different block-based chemistry, can be used in the photo-sensitive positive photoresist compositions of the present invention. The polymer preferably containing an acid-stability group is a polymer comprising a different monomer type and a co-polymer: 1) an acid which decomposes in the presence of an acid to increase the solubility in an aqueous alkaline developer solution. a monomer that is unstable, and 2) contains no unstable acid groups, and does not contain monomers that increase the basic solubility group, and/or 3) increases the solubility of the polymer's alkaline aqueous solution. body. Examples of the monomers of the type 1) are: acyclic or cyclic secondary and tertiary alkyl (meth) acrylates, such as butyl acrylate, including tert-butyl acrylate, butyl methacrylate, including -51 - This paper size applies to the National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page). Order --------- Line · Ministry of Economics Intellectual Property Bureau employee consumption cooperative printing

Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1295281 A7 B7 V. Invention Description () Tert-Butyl Methacrylate ' 3 - Oxocyclohexyl (meth) acrylate 'tetrahydropyran (A) C - Acid Cool ' 2 Methyl-Germandyl (meth) propylene _ gg , cyclohexyl (meth) acrylate, n-borneyl (meth) acrylate, (2-tetrahydropyranyl) oxynopyl acrylate, ( 2-tetrahydropyranyl)oxymethyltricyclododecanemethanol methylpropionic acid vinegar 'trimethylsulfonium s methyl (meth) acrylate* (2-tetrahydropyranyloxy)oxynopyl acrylate Ester, (2-tetrahydropyran)oxymethyltricyclododecanemethanol methyl acrylate, trimethyldecylmethyl (meth) acrylate, 〇 - /m - / p - (3 - oxygen Cyclohexyloxy)styrene, 〇— /m—/p — (1 monomethyl-1-phenylethoxy)styrene, 〇—/m — / p —tetrahydropyranyloxystyrene, 〇— /m — / P —adamantyloxystyrene, 〇—/m — / P —cyclohexyloxystyrene, 〇— /m — / p — norbornyloxystyrene, acyclic or Alkoxycarbonylstyrene, such as 〇/m — /p — ornidyl styrene, acyclic or cyclic alkoxycarbonyl styrene, like 〇 — / m — / P — butoxy alkaloid乙妇' includes P-tert-butoxycarbonylstyrene, 〇- /rn - / 3P - (3-oxocyclohexylcarbonyl)styrene, 〇 - /m - / P - (1 - methyl - 1 - 1 Phenylethoxycarbonyl styrene, 〇— /m — / p —tetrahydropyranyloxy phenyl benzene, 〇 — /m — / P — samarium oxyalkylene styrene, o—/ m — / p —cyclohexyloxy orthophenone quinone ' 0 a / m — / P — n-borne carbonyl styrene, non-cyclic or cycloalkoxycarbonyloxy styrene, like 〇 — /m — / p — Butoxycarbonyloxystyrene, including P-tert-butoxycarbonyloxystyrene, 〇— /m—/p — (3-oxocyclo-52- This paper scale applies to China National Standard (CNS) A4 size (210 X 297 mm) (Please read the note on the back and fill out this page)

1295281 A7 B7 V. INSTRUCTION DESCRIPTION (41) Hexyloxycarbonyloxy)styrene, 〇-/m — / P — (1-methyl-1,4-phenylethoxyoxy) phenyl b, 〇 -^/rn — / p —tetrahydropyranyloxycarbonyloxystyrene, 〇— /m — / p —adamantyloxycarbonyloxystyrene, 〇— /m — / p —cyclohexyloxy Carboxyoxystyrene, 〇- / m - / p - n-borneooxycarbonyloxystyrene, acyclic or cyclic alkoxycarbonylalkoxystyrene, like 〇- /m - / p - butoxy Carbomethoxymethoxystyrene, P-tert-butoxycarbonylmethoxystyrene, 〇/m—/p — (3-oxocyclohexyloxycarbonylmethoxy)styrene, 〇— / m — /p — (1 monomethyl-1-phenylethoxycarbonylmethoxy)styrene, 〇— /m — / P —tetrahydropyranyloxycarbonylmethoxystyrene, 〇— /m — / p —adamantyloxycarbonylmethoxystyrene, 〇— /m — / p —cyclohexyloxycarbonylmethoxystyrene, 〇— / m — / p — ornithoxycarbonylmethoxymethoxy Styrene, trimethyl decyl benzene * Alkenyl dimethyl (butyl) styrene silicon group, unsaturated alkyl acetate, such as isopropyl acetate, propylene, and derivatives thereof. An example of a monomer of type 1) having a low activation energy acid labile group is P- or m-(1-methoxy-l-methylethoxy)-styrene, p- or m- ( 1-methoxy-l-methylethoxy)methylstyrene, P- or m-(1-methoxy-l-methylpropoxy)styrene, p- or m- (1 —Methoxy-1-methylpropoxy)methylstyrene, P—or m—(1-methoxyethoxy)-styrene, p- or m—(1-methoxyethoxy Methyl styrene, p- or m-(1-ethoxy-l-methylethoxy)styrene, p- or m--53- This paper scale applies to China National Standard (CNS) A4 Specifications (210 X 297 mm) --------------—— (Please read the notes on the back and fill out this page) Order: -Line - Ministry of Economic Affairs Intellectual Property Bureau Staff Consumption Cooperative Printed 1295281 A7 ___B7_ V. Description of the invention (θ) II---------—— (Please read the note on the back to write this page) (1 - Ethoxy-1 Methyl Ethoxy ) monomethylstyrene, p — or m — (1 -ethoxy- 1 Monomethylpropoxy)styrene, p- or m-(1-ethoxy-l-methylpropoxy)methylstyrene, p- or m-(1-ethoxyethoxy) Styrene, p- or m-(1-ethoxyethoxy)methylstyrene, p-(1-ethoxyphenyl-ethoxy)styrene, p- or m- (1 Η-propoxy-l-methylethoxy)styrene, ρ- or m-(1-n-propoxy-l-methylethoxy)monomethylstyrene, ρ- or m — (1 - η - propoxyethoxy) phenylene, ρ - or m - (1 - η - propoxy ethoxy) monomethyl benzene, ρ - or m - (1 a different Propyl-1-methylethoxy)styrene, p- or m-(1-isopropoxy-l-methylethoxy)methylstyrene, P- or m-(1 Propyloxy)styrene, P- or m-(1-isopropoxyethoxy)methylstyrene, P- or m-(1-isopropoxy-l-methylpropane Oxy) phenylethyl olefin, P — or m — (1 -isopropoxy 1-1 methyl propyl Methylstyrene, P- or m-(1-isopropoxypropoxy)styrene, P- or m-(1-isopropoxypropoxy)methylstyrene, p - Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, printed or m - (1 - η - butoxy-l-methyl ethoxy) styrene, p - or m - (1 - η - butoxy ethoxy Styrene, ρ- or m-(1-isobutoxy-l-methylethoxy)styrene, p- or m-(1-tert-butoxy-l-methylethoxy) Styrene, p- or m-(1-n-pentyloxy-1-methylethoxy)styrene, p- or m-(1-isopentyloxy-l-methylethoxy)benzene Ethylene, ρ- or -54- not paper scale applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (introduction) m- ( 1 — η —hexyloxy-1-methylethoxy)styrene, p — or m — (1 -cyclohexyloxy- 1 -methylbutoxy)styrene, ρ — or m — (1 Trimethyl Oxyl-1 monomethylethoxy)styrene, P- or m-(1-trimethylmethyloxy-l-methylethoxy)methylstyrene, P- or m- (1 Monobenzyloxy-1-methylethoxy)styrene, P- or m-(1-benzyloxy-l-methylethoxy)methylstyrene, P- or m- ( 1-methoxy-l-methylethoxy)styrene, P- or m-(1-methoxy-l-methylethoxy)methylstyrene, P- or m- (1 Trimethyloloxyl-l-methylethoxy)styrene*P- or m-(1-trimethylmethoxyoxy-1 monomethylethoxy)methylstyrene. Other examples of alkoxyalkyl ester acid restless polymers can be found in U S - 5 2 2 5 3 1 6 and 8 2 9 7 6 6 . Examples of acetal block-based polymers can be found in US-5670299, EP-780 7 3 2, US-5627006, US-5 5 58 9 7 6 , US-5 5 5 8 9 7 1 , US-54 68 589, EP- 7 0 4 7 6 2 , EP- 7 6 2 2 0 6 , EP- 3 4 2 4 9 8 , EP- 5 5 3 7 3 7 and described in ACS Syaip. Ser. 614, Microelectronics Technology, Pp. 35-55 (1995) and J. Pho t opo 1 yiner S ci . Technol. Vo 1 . 10, N 9 . 4 (1 9 9 7 ), PP. 5 7 1 - 5 78. The polymer used in the present invention is not limited thereto. For polymers having an acetal group as an acid-unstable group, it is possible to add an acid stabilizer, as described in Η · -Τ. Schacht, P. Falcigno, N. Muenze 1, R· Schu 1 z, and A Medina , ACS Symp . ser · 7 0 6 (Micro-and Nanopatterning Polymers), p. 7 8 - 9 4, -5 5- This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 x 297 public love^ One (please read the notes on the back and fill out this page)

Booking · Line · Ϊ295281 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing A7 B7 V. Invention description (π) 19 9 7; Η·-Τ· Schacht, Ν. Muenzel, Ρ. Falcigno, Η.

Holzwarth, and J. Schneider, J. Photopolymer Science and Techno1ogy, Vo 1 · 9 (1 9 9 6 ), 57 3 - 58 6. This cross-linking system is preferred from the viewpoint of the thermal resistance standard of the photopolymer image. Examples of acid-labile monomers having a high activation energy are ρ-tert-butoxycarbonyloxystyrene, tert-butyl acrylate, tert-butyl-methacrylate, 2-methyl-2-metal Alkyl monomethacrylate, isobornyl monomethacrylate. Examples of the 2nd type of co-monomers are: aromatic vinyl monomers such as styrene, α-methylstyrene, ethoxylated styrene, cx-methylnaphthene, acenaphthylene, ethylene a cyclic compound such as vinyl norbornene, vinyl ruthenium, vinyl cyclohexane* alkyl (meth) acrylate, such as methyl methacrylate, propylene, vinyl cyclohexane, ethylene cyclohexanol, and Maleic anhydride. Examples of the comonomers of the 3) type are: vinyl aromatic compounds such as hydroxystyrene, acrylic compounds such as methacrylic acid, ethylcarbonyloxystyrene and derivatives thereof. These polymers are described, for example, in U.S. Patent No. 5, 827, 634, U.S. Patent No. 5, 562, 520, U.S. Patent No. 5, 492, 793, U.S. Pat. Other examples are crotonic acid, isocrotonic acid, 3 -butenoic acid, acrylic acid, 4-pentenoic acid, propiolic acid, 2-butyric acid, maleic acid, fumaric acid, and acetylene carboxylic acid. Polymers for use in the present invention • 56 - This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ---------------Installation --- (Please First read the notes on the back to write this page) 15. Ϊ295281 Α7 Β7 V. Invention description (0) is not limited to this. -------------- Packing - (Please read the notes on the back to write this page) - Line · Ministry of Economic Affairs Intellectual Property Bureau employees consumer cooperatives printed acid unstable monomer in polymer The content changes can be very broad and depend on the amount of other comonomers and the alkaline solubility of the deprotected polymer. Basically, the amount of acid-labile group-containing monomer in the polymer is between 5 and 60% by mole, and if the amount is too small, it will result in too low a development rate and a photoresist in the exposed region. Residual. If the amount of acid labile monomer is too high, the image of the photoresist after development is poorly defined (abrasive) and the image with narrow features cannot be resolved again and/or the photoresist is visible. It loses its adhesion to the substrate when it is like. Preferably, the copolymer having an acid labile group has a Mw value of from about 3,000 to about 200,000, more preferably from about 5,000 to about 50,000, and a molecular weight distribution of about 3 or less, more Preferably, the molecular weight distribution is about 2 or less. Non-phenolphthalein-based polymers such as alkyl acrylates (like tert-butyl acrylate or tert-butyl methacrylate) and vinyl acyclic compounds (like vinyl norbornene or vinyl cyclohexanol compounds) The copolymer may also be prepared by free radical polymerization or other conventional procedures, and suitably has a Mw value of from about 80 Å to about 50,000, and a molecular weight distribution of about 3 or less. Other co-monomers may be suitably added to control the glass transition temperature of the polymers and the like. In the present invention, two or more mixtures having an acid-unstable group may also be used, and for example, a mixture having an acid-unstable group which is very liable to be cleaved, such as an acetal group or a tetrahydropyran, may be used. Alkoxy, and a mixture of polymers with acid-cleavable groups (which are less susceptible to cleavage), such as the uncle-57- paper scale applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Α7 Β7 !295281 I. Description of the invention (w) Alkyl ester group. Different size acid-cleavable groups can be combined by mixing two or more polymers having different acid-cleavable groups, such as tert-butyl ester and 2-methyl-gold steel alkyl or 1-ethoxy-one. Ethoxy and tetrahydropyranyloxy. Mixtures of non-crosslinked or crosslinked resins can also be used. In the present invention, the number of these polymers is preferably from 30 to 99% by weight, more preferably from 50 to 98% by weight (depending on the amount of all solid components). A basic-soluble resin, or a monomer or oligomeric compound having no acid-unstable group, is further added to the composition, and 碱性 is controlled to have an alkaline solubility. Examples of polymer mixtures having different acid-unstable group-based polymers can be found in ΕΡ-780732, ΕΡ-67 9951 and US-5817444. Preferably, a monomer and an oligomerization dissolution inhibitor (a 2) are used in the present invention. The monomer or oligomerization dissolution inhibitor having an acid-unstable group for use in the present invention is a compound having at least one acid-unstable group in a molecular structure, which decomposes in the presence of an acid, and increases in alkalinity. The solubility in the aqueous solution of the developer is exemplified by alkoxymethyl ether group, tetrahydrofuryl ether, tetrahydropyranyl ether group, alkoxyethyl ether group, trityl ether group, hydrazine. Ether group, alkyl carbonate group, trityl ester group, decyl ester group, alkoxymethyl ester group, vinyl urethane group, tertiary alkyl urethane group, trityl group Amine, mercaptoester, acetal, thiol, tetrahydrofuranyl, tetrahydrofuranyl, tertiary alkyl ether, tertiary alkyl ester, and the like. The molecular weight of the acid-decomposable dissolution inhibiting compound used in the present invention is 3,000 or less, preferably from 100 to 3,000, more preferably -58 - the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297). () Please read the notes on the back to write this page) I·1 Pack--------Book---------Line· Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1529281 A7 B7 V. Description of invention (π) Ground from 20 0 to 2500. (Please read the note on the back to write this page) - Line: Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, printed monomer or oligomeric dissolution inhibitor with acid-unstable base in EP-0831369 (I) ) to (XVI) representative. Other suitable dissolution inhibitors having an acid-laboratory group can be found in US Pat. No. 5 3 56 7 52, US - 5 0 377 2 1, US - 5 0 1 5 5 54, JP - Α - 1 - 289946, JP-A - 1 1 2 9 9 9 4 7, JP - A - 2 - 2560, JP - A - 3 - 128959, JP - A - 3-15 8 855, JP - A-3-179353, JP - A-3 - 191351, JP - A - 3 - 200251, JP - A - 3-200252, JP - A - 3 - 200253, JP - A - 3 - 200255, JP - A - 3 - 259149, JP - A - 3 - 279958, JP - A - 3 - 279959, JP - A - 4 - 1650, JP - A - 4 - 1651, JP - A - 1 1260, JP - A - 4 - 12356, JP - A - 123567, JP - A - 1 — 289946, JP - A - 3-128959, JP - A - 3 - 158855, JP - A - 3 - 1 7 9353, JP - A - 3 - 191351, JP - A - 3-2 0 0 2 5 1, JP - A - 200252, JP - A - 3 A 200253, JP - A - 3 - 200254, JP - A - 3 - 200 25 5, JP - A - 3 - 259149, JP - A - 3 - 279958, JP - A — 3 — -59- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. Invention description (ice) 279959, JP - A - 4-1650, JP - A - 4 a 16 51, JP - A-1 1260, JP - A - 4 - 12356, JP - A - 4 - 12357 and Japanese Patent Application No. 3 - 33229 * 3 - 230790, 3 - 320438 * 4 - 254157, 4 104542, 4 a 107885, 4 a 107889, 4 a 152195, 4 a 2 5 4 157, 4-103215, 4 a 104542, 4 a 107885, 4-107889 and 4-152195. The composition may also comprise a specific polymeric dissolution inhibitor, such as a polyacetal, such as the compound ' or a poly-N,0-acetal as disclosed in US Pat. No. 5,354,643, such as those disclosed in US Pat. No. 5,498,506. It may be compounded with an alkali-soluble polymer or with a polymer containing an acid-unstable group which increases the solubility of the photoresist film in the developer or in combination with two types of polymers. In the present invention, a dissolution inhibitor having an acid-unstable group and an anthracene derivative of the formula I, II or III, an alkali-soluble polymer and/or an acid-labile group-containing polymer are used in combination. The dissolution inhibitor is used in an amount of from 3 to 55% by weight, preferably from 5 to 45% by weight, more preferably from 10 to 35% by weight (based on all solid content in the photosensitizing composition) Decide). Preferably, in the present invention, the use of the Chinese National Standard (CNS) A4 specification (210 X 297 mm) in the alkaline aqueous solution (a 3)-60-this paper size (please read the back note 3 first) Write this page) Order·- Line: Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed Α7 Β7 1295281 V. Invention Description (β (Please read the note on the back Η is a soluble polymer, examples of these polymers include Phenolic resin, phenolic phenolic resin, acetone-pyrophenol resin 'poly(〇-hydroxystyrene), poly(m-hydroxystyrene)' poly(P-hydroxystyrene)* hydrogenated poly(p-styrene) , halogen- or alkyl-substituted poly(hydroxystyrene), hydroxystyrene/N-substituted maleimide copolymer, 〇/p- and m/p-hydroxystyrene copolymer, 〇-alkylated poly(hydroxystyrene)' [eg 〇-methylation, 〇-(1-methoxy) ethylation, 〇-(1-ethoxy)ethylation '〇-2 - tetrahydrogen 1% sultan - line - Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperatives, printing, and - (tert-butoxycarbonyl) methylated poly(hydroxystyrene) (which has a degree of substitution from 5 to 3 moles of hydroxyl groups), 〇-m poly(hydroxystyrene) [eg 〇-醯) And 〇-(tert-butoxy)carbonylated poly(hydroxystyrene) (having a degree of radical substitution from 5 to 30 mol%), styrene/maleic anhydride copolymer, styrene/hydroxyl Styrene copolymer, α-methylstyrene/hydroxystyrene copolymer, carboxylated methacrylic resin, and derivatives thereof. Other suitable poly(meth)acrylic acid (such as poly(acrylic acid)), (meth)acrylic acid / (meth) acrylate copolymer [such as acrylic acid / methacrylate copolymer, methacrylic acid / methyl methacrylate copolymer, or methacrylic acid / methyl methacrylate / tert-butyl methacrylate copolymer], ( A) acrylic acid/olefin copolymer [such as acrylic acid/ethylene copolymer], (meth)acrylic acid / (meth) acrylamide copolymer [such as acrylic acid / acrylamide copolymer], (meth) acrylic acid / ethylene chloride copolymer [such as acrylic acid/ethylene chloride Polymer], (meth)acrylic acid/ethylene acetate copolymer [such as acrylic acid / -61- This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. Invention description (# Ethylene acetate copolymer], maleic acid/vinyl ether copolymer [such as maleic acid / methyl vinyl ether copolymer], maleic acid monoester / methyl vinyl ester copolymer [such as a maleic acid methyl ester/methyl vinyl ether copolymer], a maleic acid/(meth)acrylic acid copolymer [such as a maleic acid/acrylic acid copolymer or a maleic acid/methacrylic acid) Copolymer], maleic acid/(meth)acrylate copolymer (such as maleic acid/methacrylate copolymer), maleic acid/ethylene chloride copolymer, maleic acid / ethylene acetate copolymer and maleic acid / olefin copolymer [such as maleic acid / ethylene copolymer and maleic acid / 1-chloropropene copolymer]. However, the alkali-soluble polymer used in the present invention should not be limited to these examples. Particularly preferred base-soluble polymer (a 3) is a phenolic resin, poly(anthracene-hydroxystyrene), poly(m-hydroxystyrene), poly(p-hydroxystyrene), and individual hydroxystyrene monomers. Copolymers, for example, and P-vinylcyclohexyl, alkyl-substituted poly(hydroxystyrene), partially oxime- or m-alkylated and oxime- and m-thiolated poly(hydroxystyrene) , a styrene/hydroxystyrene copolymer, and an α-methylstyrene/hydroxystyrene copolymer. The phenolic resin can be obtained by adding one or more specific monomers as a main component and one or more aldehydes in the presence of an acid catalyst to form a condensation reaction. Examples of the bases which can be used for the preparation of the alkali-soluble resin include hydroxylated aromatic compounds such as phenol, cresol, such as m-cresol, cresol and cresol, and xylenols such as 2,5. Xylenol, 3,5-xylenol, 3, 4-xylenol, and 2,3-xylenol, alkoxyphenols, such as P-A-6 2 ~ This paper scale applies to Chinese national standards (CNS) A4 specification (210 X 297 mm) (Please read the note on the back and fill out this page) Order-------------Line « Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative 1,295,281 A7 B7 V. Description of the invention (θ) oxyphenol, m-methoxyphenol, 3,5-yl- 4-methyl, m-ethoxy, oxy, P-propoxy Stuffed, m-butoxy, dialkylphenols, such as 2-methyl-4-aromatic compounds, including m-chlorinated phenol, bishydroxybiphenylbisphenol A, phenyl. These compounds can be used alone or as an anthraquinone. It can be used as a master example for the preparation of phenolic resins. And phenolic compound polycondensation reaction preparation includes formaldehyde, hydrazine-formaldehyde, acetaldehyde, propionaldehyde α-phenylpropanal, /3-phenylpropanal, nonylbenzaldehyde, hydrazine-hydroxybenzaldehyde, hydrazine-benzaldehyde, Ρ - Benzyl chloride, hydrazine - nitroformaldehyde, hydrazine - methyl benzaldehyde, m-methyl aldehyde, P - ethyl benzaldehyde, ρ - n-butyraldehyde, acetaldehyde, and derived from these two Methoxyphenol, 2 P-ethoxyphenol, base, and ρ-butyl isopropyl phenol, P-chlorophenol, two or more monomers and phenolic resin, benzaldehyde-hydroxybenzene chlorination Benzylbenzaldehyde benzaldehyde, acetal of phenylformaldehyde, and its phenol, diphenol, the components are not limited to aldehydes, phenylformaldehyde, aldehyde, m, m-ρ-甲,α一,像Mixture of chloro-methoxy m-propoxy phenol, hydroxy hydrazine-chloro and naphthol. Examples of the above acetaldehyde, m - nitrophenyl benzofuran acetaldehyde, please read the back item

t Ministry of Economic Affairs Intellectual Property Bureau employees consumption cooperatives printed two rich ο ο 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 False, the strong hydrogen quantum, the low-class brackets are divided into large and too large, and the average value is too small. The weight of the weight will be like that of the media. The thinner is the acid and fat pseudo-zone. Two trees. Light ο 佳 acetal ο ο ο ο ο ο ο ο ο ο From the beginning, it is ο 醒 醒 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 (210 X 297 mm) 1295281 Α7 Β7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (6 〇 molecular weight is preferably from 2000 to 20000. Upper sputum as alkaline-soluble polymer ( The non-phenolic resin) (hydroxy styrene) and derivatives and copolymers thereof each have a weight average molecular weight of 2,000 or more, preferably from 4,000 to 200,000, more preferably from 5,000 to 50,000. From the viewpoint of obtaining a polymer film having an improved heat resistance, the weight average molecular weight thereof is desirably at least 50,000 or higher. In the present invention, the weight average molecular weight means gel permeation chromatography, and K polymerization. The value obtained by styrene correction. In the present invention, the alkali-soluble polymer can be used as a mixture of two or more polymers, using a base-soluble polymer and having a decomposition under the action of an acid. Solubility in alkaline imaging agents In the case of a group-based polymer mixture, the alkali-soluble polymer is preferably added in an amount of up to 80% by weight, more preferably up to 60% by weight, most preferably up to 40% by weight. Percentage (calculated based on the total amount of photo-sensitive composition, excluding solvent). An amount exceeding 80% by weight is undesirable because the thickness of the resist image is severely degraded, resulting in poor image quality, resolution Low. In the case of using a soluble polymer together with a dissolution inhibitor, it does not contain a polymer which has a solubility group under the action of an acid and enhances the solubility group in the alkaline imaging solution, and the alkali is soluble. The amount of the polymer is preferably from 40% to 90% by weight, more preferably from 50 to 8% by weight, most preferably from 60 to 80% by weight. 0% by weight, undesired results, such as reduced sensitivity, etc. On the other hand, if it exceeds 90% by weight -64- (please read the notes on the back - R--- f) taj· --Line - This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 PCT) 1295281 A7 B7 V. Inventive Note (w) The film thickness of the photoresist image is seriously reduced, resulting in poor resolution and image reprint quality. 'In the positive photoresist of the present invention, Formula I The amount of the II, II and III hydrazine derivatives (ingredient (b)) is preferably from 0. 01% to 20% by weight (depending on the total weight of all solid components of the photoresist). According to the present invention, The use of an anthracene derivative (which operates on the principle of removing a protecting group on a polymer) in a chemical amplification system generally produces a positive photoresist. In many applications, *positive photoresists are more reflective than negative photoresists, especially their resolution. However, in order to combine the advantages of the high resolution of the positive photoresist and the nature of the negative photoresist, it is also advantageous to use a positive photoresist mechanism to produce a negative image. This can be achieved by introducing a so-called image-reverse step, as described in E P -3 6 1 0 0 6 . For this purpose, the image-illuminating material is subjected to a treatment such as a gas alkali before the development step, such that the image is neutralized with the acid produced, and then, the second illumination (all regions), followed by the subsequent heat treatment. Then, the traditional method is used to develop a negative image. An acid-sensitive component capable of producing a negative photoresist, particularly when citrate catalyzed (such as an acid formed when a compound of formula I, II or III is illuminated) can be produced with itself and/or with other components of one or more of the constituents. The compound of the crosslinking reaction, such as a conventional acid-hardenable resin, such as, for example, acrylic acid* polyester, alkyd resin, melamine, urea, epoxy group and phenol resin, or a mixture thereof. Amine resins, phenol resins and epoxy resins are particularly suitable. This type of acid-hardenable resin is generally known and described, for example, Ulimann's Encyclopadie der -6 5 - This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 297 297 mm) ---- ----------装--- (Please read the note on the back? Write this page) Order ·- - Line _ Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1295281 A7 factory __B7__ five , invention description (A) technischen C he mi ew (Ullmanns Enceclopedia of (please read the back of the note first and then fill out this page)

Technical Chemistry), 4th Edition, Vol. 15 (1978), P. 6 1 3-628. The crosslinker component is typically present at a concentration of from 2 to 40, preferably from 5 to 30 weight percent (calculated based on the total solids composition of the negative optical composition). Accordingly, the present invention includes a chemically amplified negative, alkali-developable photoresist as a specific embodiment comprising: (a4)-alkali-soluble resin as a binder, (a5) when K-acid catalyzed A component which is a cross-linking reaction with itself and/or with a binder, and (b) a derivative of formula I, II or III as a photo-sensitive acid supply. This composition may additionally include other photo-sensitive acid supply agents and/or (c) other additives in addition to component (b). The Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperative, prints as an acid-hardenable resin (a 5 ), preferably an amine-based resin, such as a non-etherified or etherified melamine, urea, acridine or biuret resin. In particular, methyl melamine resin or butyl melamine resin (corresponding to glycoluril and urea _). In this context, the term "resin" is used to refer to a mixture of traditional artisans (generally including oligomers) and pure and high purity compounds. N-hexa(methoxymethyl) melamine and tetramethoxymethyl glycoluril, and hydrazine, Ν'-dimethoxymethylurea ketone are the most preferred acid-hardenable resins. The concentration of the compound of formula I, II or III in the negative photoresist is generally from 0♦ 1 to 30, preferably up to 20% by weight (according to the group -66**, this paper scale applies to the Chinese National Standard (CNS) A4. Specifications (210 X 297 mm) 1295281 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed 5, invention description (depending on the weight of all solid components in the product. From 1 to 15 weight percent is particularly good.' The negative composition may suitably comprise a film to form a polymeric binder (a 4). The binder is preferably a base-soluble phenolic resin, suitable for this purpose, for example, derived from aldehydes and phenols. Phenolic resins, such as acetaldehyde or furaldehyde, in particular from formaldehyde, and unsubstituted phenols, singly or dichloro-substituted phenols, like P-chlorinated phenols, by (:1 - -9 alkyl single a substituted phenol, such as 〇-, m- or p-cresol, each _ xylenol, such as P-tert-butyl phenol, P-nonyl phenol, p-phenyl phenol, resorcinol , bis(4-hydroxyphenyl)methane or 2,2-bis(4-hydroxyphenyl)propane. Also suitable a homo- or co-polymer based on an ethylenically unsaturated phenol, such as a homopolymer of ethylene mono- and 1-propenyl-substituted phenol, such as ρ-vinylphenol or hydrazine-(1-propenyl) phenol or these phenols and one or A plurality of copolymers of ethylene and no materials, such as styrene. The amount of the binder is generally from 30 to 95% by weight, preferably from 40 to 80% by weight. Particularly preferred negative photoresist compositions include 0 · 5 to 15 5 % by weight of the hydrazine derivative of the formula I, II or III (ingredient (b )), from 40 to 99% by weight of the phenol resin as a binder (ingredient (a 4 ), for example, the above-mentioned bonding a kind of agent, and a melamine resin (component (a5)) as a crosslinking agent from 0.5 to 30% by weight, wherein the percentage is calculated based on the solid content of the composition. Furfural phenol resin, or special aggregation Ethylphenol is used as a binder to obtain a negative photo-67' with a particularly good quality. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 public). (Please read the notes on the back Μ Install i — π write this page) Order: • Line - A7 B7 1295281 Five DESCRIPTION OF THE INVENTION () Agents Anthracene derivatives can also be used as acid generators (which can be photochemically activated), and are used in the acid-catalyzed crosslinking of poly(oxiranium)methacrylate in a negative photoresist system. This cross-linking reaction is described, for example, in Chae et al. in Pollimo 1 9 9 3 , 1 7 (3), 2 9 2 正. The positive and negative photoresist compositions of the present invention are in addition to the light of formulas I, II and III. In addition to the sensitive acid supply, it further includes other photo-sensitive acid supply compound (bl), other additives (c), other photoinitiators (d), and/or sensitizers (e). Accordingly, the subject matter of the present invention is also a chemically amplified photoresist composition as described above, except for the components (a) and (b), or the components (al), (a 2 ), (a3) and (b), or In addition to the components (a4), (a5) and (b), other additives (c), other photo-sensitive acid supply compounds (bl), other photoinitiators (d), and/or sensitizers (e) are included. Among the positive and negative photoresists, the anthracene derivatives of the present invention can also be used together with other conventional photolatent acids (b 1 ), such as salt, 6-nitrobenzylsulfonate, disulfonyl diazo. A methane compound, a fluorine-containing oxime sulfonate compound, and the like. Examples of conventional photolatent acids that can be used in chemically amplified photoresists are described in U.S. Patent No. 5,713, 364, U.S. Patent No. 5,800,964, issued to A.S. Pat. In case the photolatent acid mixture is used in the photoresist composition of the present invention, the formula I * II or III 肟 derivatives and other photolating-6 8 - paper scales are applicable to the Chinese National Standard (CNS) A4 specification (210 X 297). )) -------------装--- (Please read the note on the back to write this page) Order · Line: Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1295281 Α7 Β7 5 DESCRIPTION OF THE INVENTION (Μ) The weight ratio of the acid (b 1 ) in the mixture is preferably from 1:9 9 to 9 9 ··1. Examples of suitable photolatent acids for use in combination with the compounds of formula I, I I and I I I are: (1) key salt compounds, for example: iodine salt, sulfonium salt, phosphonium salt, diazonium salt, pyridinium salt. Preferred are diphenyliodonium trifluoromethanesulfonate, diphenyliodonium sulfonate, triphenyl iodonium dodecylbenzenesulfonate, triphenylsulfonium trifluoromethanesulfonate , triphenylsulfonium hexafluoroantimonate, diphenyliodide chromium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, (hydroxyphenyl)benzylmethylindole tosylate and the like. Particularly preferred are triphenylsulfonium trifluoromethanesulfonate, triphenyliodonium hexafluoroantimonate. (2) Halogen-containing compound A halogenated alkyl heterocyclic compound, a halogenated alkyl hydrocarbon, and the like. Preferred is (trichloromethyl)-s-triazine derivative, such as phenyl-bis(methyl chloride)-s-triazine, methylphenyl-bis(trichloromethyl)-S - triazine, Tsai, mono-(trichloromethyl)-S-triazine, and the like; 1, 1 bis (4 phenyl chloride) - 2,2,2-trichloroethane; And similar. (3) A maple compound such as bismuth-boron boron, bismuth-sulfonium boron and its ?-diazo derivative and the like. Preferred are benzoquinone phenyl, mesitylene benzoquinone, bis(phenylsulfonyl)methane, bis(phenylsulfonyl)diazomethane. (4) Sulfonate compounds, for example -69- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) s Please read the back of the note first. Printed by the Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative

1295281 A7 B7_ V. Description of the invention (required) Alkyl sulfonate, halogenated alkyl sulfonate, aryl sulfonate, imido sulfonate, sulfhydryl sulfonate and the like. Preferred guanamine sulfonate compounds are, for example, N-(trifluoromethanesulfonyloxy)butaneimine, N-(trifluoromethylsulfonyloxy)peptide quinone imine, N —(trifluoromethylsulfonyloxy)naphthylimine, N —(trifluoromethylsulfonyloxy)diphenylmethylenediimide, N—(methylsulfonyltrifluoride) Oxy) abicyclo-[2 •2·1]-hepta-5-ene-2,3-dicarboxyarsenine, N — (trifluoromethanesulfonyloxy)-7-oxabicyclo- [2·2·1] 1-gly-5-ene-2,3-dicarboxy-imine, N —(trifluoromethanesulfonyloxy)-7-oxabicyclo-[2·2·1 〕一庚一5 — ene-2,3-dicarboxyarsenine, Ν — (trifluoromethanesulfonyloxy)-bicyclo[2 · 2 · 1]-heptane-5,6-oxy a 2,3-dicarboxyarmine imine-(mercaptosulfonyloxy)butaneimine, anthracene-(fluorenylsulfonyloxy)peptidinium imine, anthracene - (mercaptosulfonyloxy) Naphthoquinone imine, Ν-(fluorenylsulfonyloxy)diphenylmethylenediimide, anthracene — (fluorenylsulfonyloxy) double [2 · 2 ♦ 1]-gly-5-ene-2,3-dicarboxyarsenine, Ν-(mercaptosulfonyloxy)-7-oxabicyclo-[2·2. 1]-g a 5-alkenyl-2,3-dicarboxyarmine imine, Ν-(mercaptosulfonyloxy)-7-oxabicyclo-[2'2*1]-g-g-5-women-2,3 — Bisporin imine, Ν — (孩基醯醯oxy)bicyclo[2·2·1]-g-a-5,6-oxy-2,3-dicarboquinone imine, Ν—(4一甲Phenyl sulfonyloxy) butyl quinone imine, Ν - (4-methylphenyl sulfonyloxy) timinoimine, Ν - (4 - This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the notes on the back and fill out this page) .3⁄4 Order---------Line· Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1295281 Α7 Β7 V. Invention Description () Methylphenylsulfonyloxy)naphthylimine, N-(4-methylphenylsulfonyl------------- armored - (please read the back first) Note 3 Write this page) 醯oxy)naphthyl quinone imine, N—(4-methylphenylsulfonyloxy)diphenyl cis Ethylidene, N-(4-methylphenylsulfonyloxy)-bicyclo-[2 ♦ 2 ♦ 1]-g--5-ene-2,3-dicarboxyarmine, N—(4 —methylphenylsulfonyloxy)-7-oxabicyclo-[2 • 2,1]-hepta-5-ene-2,3-dicarboxyindoleimine, N-(4-methylphenyl) Sulfoxyloxy)-bicyclic-[2·2·1]-hepta-5,6-oxy-2,3-diimine, hydrazine-(2-trifluoromethylphenylsulfonate Butyldiamine, hydrazine - (2-trifluoromethylphenylsulfonyloxy)naphthylimine, hydrazine - (2-trifluoromethylphenylsulfonyloxy) diphenyl Isobutyleneimine, Ν-(2-trifluoromethylphenylsulfonyloxy)-bicyclo-[2·2·1]-g--5-ene-2,3-dicarboxyfluorene Amine, hydrazine - (2 - trifluoromethylphenylsulfonyloxy)-7-oxabicyclo-[2.2.1]-gly-5-ene-2,3-dicarboxyarmine, hydrazine - (2-trimethylphenylsulfonyloxy)-bicyclo[2*2·1]-hepta-5,6-oxy-2,3-dicarboximine, and Analogs. Other suitable sulfonate compounds are printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs, such as benzamidine benzethane tosylate, pyrogallol tri-trifluoromethanesulfonate, eschar Phenol methanesulfonate triester, nitrobenzyl-9,10-diethoxyindole-2-sulfonate, α-(4-methylsulfonyloxyimino)-benzylcyano Compound, α (4-toluene-sulfonyloxyimino)-tetramethyloxybenzyl cyanide, α-(4-toluene-oximeoxy-7- 1- paper scale applicable to China Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. Description of invention) Amino) 2- 2 - thiomethyl fluoride, α - (methanesulfonyloxyimino)-1 ring Hexenylacetonitrile, α-(butylsulfooxyimino)-1,4-cyclopentene acetonitrile, (4-methylsulfonyloxyimido-cyclohexyl 2,5-diene) benzene Benzyl acetonitrile, (5-methylsulfonyloxyimido- 5 Η-thiophene-2- 2 fork)-phenyl-acetonitrile, (5-methylsulfonyloxyimino- 5 Η-thiophene 2-2-fork)-(2-methylphenyl)-acetonitrile, (5-methylsulfonyloxyimido-5-thiophene-2-one)-(2-chlorophenyl)-acetonitrile and analog. In the photosensitive resin composition of the present invention, particularly preferred sulfonium salt compounds include pyrogallol methanesulfonate, fluorene-(trifluoromethanesulfonyloxy)bicyclo-[2 ♦ 2 · 1] 1-gly-5-ene-2,3-dicarboxyarsenine, anthracene (fluorenylsulfonyloxy)naphthylimine, anthracene - (2-trifluoromethylphenylsulfonyloxy) peptide Yttrium imine, hydrazine - (trifluoromethanesulfonyloxy)-bicyclo-[2·2·1]-gly-5-ene-2,3-dicarboxyarmine, hydrazine-(mercaptosulfonate)醯oxy)cainyl imine, Ν-(2-trifluoromethylphenylsulfonyloxy)titanium-imine and the like. (5) a fluorenone diazide sulfonate compound of a polyhydroxy compound, preferably a compound having a stilbene diazide sulfonic acid group such as 1,2-benzoacneone Azide-4-sulfonyl, 1,2-naphthylquinonediazide-4-sulfonyl, 1,2-naphthylquinonediazide-5-sulfonyl, 1,2-naphthylquinone Di-II-nitro-6-sulfonyl or a similar group. A particularly good compound is -72- having a 1,2-naphthylquinonediazide-4 sulfonyl group or a 1,4-naphthoquinone di II nitride-5-sulfonyl group. National Standard (CNS) A4 Specification (210 X 297 mm) ------------- Pack--- (Please read the notes on the back first > Write this page) ιδ· - Line - Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, Printed 1295281 A7 B7 V. Inventions () Compounds. Particularly suitable are (poly)hydroxyphenyl aryl ketone 1,2-nonanone diazide sulfonate, like 2,3,4-trihydroxybenzophenyl hydrazine, 2,4,6-trihydroxybenzene Benzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',3,4-tetrahydroxybenzophenone, 2,3, 4,4> tetrahydroxybenzobenzene Ketone, 2,2',4,4'-tetrahydroxybenzobenzoquinone, 2,2',3,4,47-pentahydroxybenzophenone, 2,2',3,2,6'-five Hydroxybenzophenone, 2,3,3/,4,4, ,5'-hexahydroxybenzobenzoquinone, 2,3',4,4',5',6-hexahydroxybenzophenone and Analog; bis-((poly)hydroxyphenyl]alkyl 1,2-quinolone diazide sulfonate, like bis(4-hydroxyphenyl)ethane, bis(2,4-dihydroxyphenyl) Ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(2,4-dihydroxyphenyl)propane, 2,2-bis-(2,3,4-trihydroxyl) Phenyl)propane and the like; 1,2-quinonediazide sulfonate of (poly)hydroxyphenylalkane, like 4,4'-dihydroxytriphenylmethane, 4, 4, 4 three Hydroxyphenylmethane, 4,4',5,5'-tetramethyl, 2,2',2〃-trihydroxytriphenylmethane, 2,2,5,5'-tetramethyl-4, 4〃-trihydroxytriphenylmethane, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1, 1 a bis(4-hydroxyphenyl)-l-(4-mono-1-(p-phenyl)-l-methylethyl]phenyl)ethane and the like; (poly)hydroxyphenylxantane 1,2 - anthrone diazonium sulfonate, like 2,4,4-trimethyl- 2', 4'-73- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297厘) -------------装--- (Please read the note on the back to write this page) Order · · .. Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1295281 A7 B7 Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives, Printing 5, Invention Description (1-7-trihydroxy-2-phenyl-phenyl-ane, 2,4,4-trimethyl-7-pentahydroxy- 2-phenylflavan, And 2 / 5 6 of its analogs. The positive and negative photoresist compositions of the present invention have a variety of traditions Additives for photoresists (conventional quantities known to those skilled in the art, plasticizers for additives, surfactants, flow modifiers, thixotropic agents, dyes, fillers, dissolution plus sensitizers and organic base compounds) Other examples which may be used in the present base compound are strong base compounds which are specific to phenols. These compounds may be in the ionic form of the ionic form. Preferred organic base compounds having two or more molecules each having less than preferably contain at least one Compounds having a substituted or unnitrogen-containing ring structure, and examples having at least these preferred compounds include acridine, pyridine, aminopyrrolidine, oxazole, imidazole, pyridyl, imidazoline, pyrazoline, piperazine, amine group Suitable are unsubstituted compounds, or substituents thereof include an amine group, an aminoalkyl group, an alkylamino group, an alkyl alkoxy group, a decyloxy group, and a cyano group. Particularly preferred organic base compounds are optional), examples of which are dyeing wetting agents, speeding agents, acid inventing photoreceptors, especially, for example, four nitrogen-containing bases and chemical ring-substituted amine monoalkylamine aminopyridines , pyridazine, and alkyl substituted amino group, aryl, aromatic special case 1 1 dimethyl acridine 1, 1 , 3, 3 - 4 is included in the amount of the material, the adhesion is enlarged The composition of the agent is a nitrogen-based group containing an alkylammonium compound, and a group, an amine group, a pyridylamino group derivative, an amine group, an aryloxy group, a methyl group, or a material, a booster, a agent. , photoorganic organic nitrogen alkalized salt or non, of which atoms, - compounds. Alkylpyridyl, 嘌呤? . Preferred base, aryl, hydroxyacridine, 2 - please read the back of the note first

t 74- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. Description of invention (71 Aminopyridine, 3-aminopyridine, 4-aminopyridine, pyridyl, 4-monomethylaminopyridine, 2-±:ethyl-(aminomethyl)pyridine, 2-amino-3-methyl-tetramethylpyridine, 2-amino-5-methyl 6-methylpyridine, 3 aminoethylpyridazine, N-pyridinidine, pyridine piperidine, 2-(2 4 monoamine, 3-aminopyrrolidine, piperazine N-(2-aminoethyl) Monomethyl group ,$,4 呢 (2-aminoethyl)pyrrolidine, pyrazole, 3 2 -diaminopyridinium, pyridine, 2 aminoethylethyl)methylamine pyridine, 2 2 -amine-aminopyridine piperazine, 4-monoamine- 2,2,6,6-iminopiperidine-amine-amine 5 1 monomethyl hydrazine, please read the back notes and refill Benzazole, 5-amino-3-methyl-2-(aminomethyl)-5-pyrimidine, 4,6-dihydroxypyrimidin-1-P-methylpiperazine-(2,2-amine N-aminomorpholine, and N Examples of suitable organic base compounds are described in US 5609989, US 6 2 2 0 7, 3 18 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed EP - 7 6 119 Inventions are used separately. Usually 0 ♦ 0 1 adult (not The amount is not 9 8 and the US-organic compound and or two or more are from 0 · 0 0 to 5 parts by weight (including solvent)), the DE - 4 3 0 5 4 9 8 5 0 of the present invention can be obtained. Limited to the combination of these examples, containing 1 to 10 parts by weight per 100 parts of the weight of the effect of its use. Another toluene pyrazole, pyrazine, pyrimidine, 2,4 diamine pyrazoline, 3 - Pyrazoline ethyl)morpholine. 逑DE-4408 5 5 5 6 7 3 4, 6 0 6 9,EP-6. However, it is suitable for the use of nitrogen-base compound nitrogen-base compounds. The preferred amount of light-sensitive resin group is less than 0·0 0 1 part, if the usage exceeds -75-, the paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. INSTRUCTION DESCRIPTION (π) If 10 parts by weight is used, it is easy to cause a decrease in photosensitivity and display in an unexposed area. The composition of the invention may further comprise an alkaline organic compound (suicide base) which decomposes under actinic radiation, as described in EP-710885, US5663035, US-5595855, US-5525453 And EP - 6 1 1 9 9 5 〇 Examples of the dye (c) suitable for use in the composition of the present invention are oil-soluble dyes and basic dyes such as Oil Yellow #101, Oil Yellow #103, Oil Pink ¢312, Oil Green GB, Oil Blue BOS, Oil Blue #603, Oil Black BY, Oil Black BS5 Oil Black T-505 (all manufactured by Orient Chemical Industries Ltd., Japan), Crystal violet (CI 4 2 5 5 5 ), A Base purple (CI 4 2 5 3 5 ), rhodamine B (Cl 4 5 1 7 0 B), milk green (Cl 4 2 0 0 0), and methyl blue (Cl 52015). The optical sensitizer (e) may further be added with M sensitizing photolatent acid to prevent absorption of longer wavelengths in the ultraviolet ray outer region, such that the photosensitive composition of the present invention is, for example, i-line or g-line radiation Sensitive. Examples of suitable optical sensitizers include benzophenone, P, P'-tetramethyldiaminobenzobenzene_, p, P'-tetraethylethylaminobenzobenzoate, thioxanthone ), 2 - chlorphenone ketone, ketone, K, dioxin, phenothiazine, benzamidine, acridine orange, benzoflavan, cetyl T, 9 , 10 - diphenyl hydrazine , 9-fluorone, acetophenone, phenanthrene, 2-nitrofluoro, 5-nitro-ene, benzopyrene, 2-chloro-4-nitroaniline-76- This paper scale applies to China Standard (CNS) A4 specification (210 X 297 public) (Please read the note on the back and fill out this page) !!!1 Book! — II---Line. Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1295281 A7 B7 V. Invention Description ( ), N-Ethyl P-Nitroaniline, P-Nitroaniline, N-Ethyl-4 Mononitro-1,4-naphthylamine, bitteramine, anthraquinone, 2-ethylanthracene, 2-tert-butyl-butyl guanidine, 1,2-benzoquinone, 3-methyl-1,3-two吖1,9 benzophenone, diphenylacetone, 1,2-naphthoquinone, 3 coumarin derivative, 3,3'-carbonyl bis(5,7-dimethoxy-carbonyl coumarin素), 3 - (aryl carbene) thiazoline, eos in, rhodamine, erythrosine and coronene. However, suitable photosensitizers are not limited to these examples. These optical sensitizers can be used as a far-ultraviolet light emitted by the light absorbing agent Μ absorbing light source. In this case, the light absorbing agent reduces the light reflected by the substrate and reduces the influence of multiple reflections in the photoresist film. Effect of Waves 0 Other suitable additives (C) are // Acid-amplifiers // f Compounds that accelerate acid formation or increase acid concentration These compounds can also be combined with Formula I, II or III of the present invention. % of negative photoresist or in imaging systems, and for use in coating applications. These acid amplification agents are described, for example, in Ar i in it su , K . eta 1 . J. Photopolyra S ci· tec hn 〇 1. 1995 8, pp 43; Kudo, K. e al • 9 J • Photopolyra. S ci · T ec hnο 1 . 1 9 9 5, 8 , pp 45 ; Ic hi mur a 9 K . eta 1 · c hem : Letters 1995 5 PP 5 5 1 c ) When the photo-sensitive composition gtg of the present invention is applied to a substrate, a*·Π1 often dissolves the composition Preferred examples of these solvents in a suitable solvent include ethylene di-77- this paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ------------1 % (Please read the note on the back and then fill out this page) Order---------Line· Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1295281 A7 B7 V. Invention Description (?〇chloride, ring Hexanone, cyclopentanone, 2-heptanone, 7-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate ,2-ethoxyethyl acetate, 2-ethoxyethanol, diethyl glycol dimethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl Ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxy propionate, ethyl ethoxy propionate, methyl pyruvate, B Pyruvate, propylpyruvate, N,N-dimethylformamide, dimethyl mill, N-methylpyrrolidinium, and tetrahydrofuran. These solvents may be used singly or in combination. Preferred examples of such solvents are esters such as 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl methoxypropionate Ethyl ethoxy propionate and ethyl lactate. The use of these solvents is advantageous because the formula I, II or III hydrazine derivatives of the present invention are well compatible and have a better solubility therein. The surfactant may be added to the solvent. Examples of suitable surfactants include nonionic surfactants, such as polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene acetonitrile, and polyoxyethylene olefinic ether; polyoxyethylene alkyl aryl ethers, such as polyoxyethylene octyl phenol ether and polyoxyethylene decyl phenol ether; polyoxygen Ethylene/polyoxypropylene block copolymers, sorbose/fatty acid esters such as sorbitan monolaurate, sorbose monopalmitate, sorbityl monostearate, sorbitan monooleate , sorbitan trioleate; fluorochemical surfactants, like F-top EF301, EF303 and EF352 (made by New Akita Chemical Company, Japan -7 8 - This paper scale applies to China National Standard (CNS) A4 specification (210 χ 297 mm) -------------% (Please read the notes on the back and fill out this page) Order---------Line·Ministry of Intellectual Property Consumer Cooperatives Printed 1292851 A7 B7 V. Invention Description (%) (Please read the notes on the back and fill out this page) Make) oMegafac F171 and F17.3 (by Dain Ippon Ink & Chemicals, Inc., manufactured by Japan, Fluorad FC430 and FC43 1 (manufactured by Sunlit Ohio 3 ML td, Japan), Asahi Guard AG7 1 0 and Surf 1 οn S- 3 8 2 , SC 101 , SC 102, SC 103, SC104, SC105 and SC106 (manufactured by Asahi Grass Col., Ltd., Japan); organic decane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd., Japan); and propylene Acid or acrylic acid (co)polymer Poly-flow Now, 75 and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd., Japan). The amount of the interface active agent to be added is usually 2 parts by weight or less, preferably 5% by weight or less (per 100 parts by weight of the solid content of the composition of the present invention). The surfactants may be used singly or in combination of two or more. The Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing solution is a uniform coating method applied to the substrate, such as spin coating, impregnation, knife coating Uni Fe coating, curtain pour ing Techniques), brush application, spray and reverse drum coating. It is also possible to apply this photo-sensitive layer to a temporary flexible support and then apply the final substrate by coating transfer (laminating). The amount applied (coating thickness) and the nature of the substrate (coated substrate) are based on the desired field of application; the thickness of the coating ranges mainly from about 0 ♦ Ο 1 μm to over 100 μm. After the coating operation, the solvent is generally removed by heating, and as a result, a photoresist is formed on the substrate. The drying temperature must be lower than the specific composition of the photoresist. -7 9- This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) A7 B7 !295281 V. Invention description (Supplement) ----- ----------- (Please read the notes on the back first ^^ Write this page) The temperature of the reaction or decomposition, in general, the drying temperature is in the range of 603⁄4 to 160. The photoresist coating is then illuminated in the manner of an image. The meaning of illuminating 〃 according to an image includes illuminating a predetermined pattern using an actinic ray, that is, illuminating a reticle containing a predetermined pattern, such as a transparent, and using a laser beam on the coated substrate. Moving the illumination upwards, for example under computer control, produces an image. Another way to make an image is to use interference from a beam or image like a halographic application. It is also possible to use a photomask made of liquid crystal which can be positioned by a pixel to produce a digital image as described in A. Bertsch; JY Jezequel; J. C. Andre in Journal of Photochemistry and Photobiology A: Chemistry 1997, 10 7 p275-281 and Κ· P . N i co 1 ay in Offset Printing 1 9 9 7 , 6 , P3 4 - 3 7 〇• Line: After the illumination of the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs (if necessary, After the heat treatment, the unexposed portion of the composition (in the case of a positive photoresist) or the irradiated portion (in the case of a negative photoresist) is a conventional method, which is removed using an imaging agent. It usually takes a while before the imaging step to allow the acid-sensitive component of the photoresist to react. In order to accelerate the reaction, and the difference in solubility of the photoresist coating in the developer between the irradiated portion and the unirradiated portion is sufficiently developed, it is preferred to heat the coating before development. Heating can also be carried out at the time of illumination or at the time of illumination, preferably at a temperature of from 60 to 160 Torr. The time is based on the heating method. If necessary, the best time can be obtained by the Chinese National Standard (CNS) A4 specification (210 X 297 mm). Cooperatives Printed 1295281 A7 B7 V. INSTRUCTIONS (π) People are easily obtained by repeated tests, usually from a few seconds to a few minutes. For example, when using a hot plate, it is very suitable from 10 to 300 seconds. When using an air suction oven, it is suitable from 1 to 30 minutes. It is important that the latent acid supply of the present invention remains stable at the unilluminated address of the photoresist under processing conditions of the upper crucible. The coating is then imaged, and the portion of the coating that is more soluble in the developer after illumination is removed, if necessary, with a slight agitation at the work site, or a gentle brushing in the developer bath. Overlay, or spray imaging, speeds up the processing steps. Alkaline aqueous imaging agents traditionally used in photoresist technology can be used, for example, for imaging. These imaging agents include sodium or potassium hydroxides, cypress corresponding carbonates, hydrogencarbonates, citrates or metal citrates* but preferably metal-free bases like ammonia or amines such as ethylamine. , n-propylamine, diethylamine, di-n-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, such as dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, such as tetramethyl hydroxide Ammonium or tetraethylammonium hydroxide. This developer solution is typically up to 0 ♦ 5N, but is usually diluted prior to use in a suitable manner. For example, a solution having an equivalent molar concentration of about 0 ♦ 1 - 0 · 3 is very suitable. The choice of imaging agent will depend on the nature of the photohardenable surface coating, especially depending on the nature of the adhesive or resulting photodegradable product. The aqueous solution of the developer may also include a relatively small amount of a wetting agent, and/or an organic solvent, if desired. The basic organic solvent which can be added to the developer liquid is, for example, cyclohexanone, 2-ethoxyethanol*toluene, acetone, isopropanol* and a mixture of two or more of these solvents. The typical aqueous/organic developer system is base -8 1 - this paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) "

1295281 A7 B7 V. INSTRUCTIONS (Μ) on Butyicellosolve RTΜ/ Water. ---------------I--- (Please read the note on the back first to write this page) The present invention also relates to a method of preparing a photoresist, including: (1) Applying the above composition to a substrate; (2) post-baking the composition at a temperature of 60 ° C and 160 ° C; (3) a light source having a wavelength of 150 nm and an I 500 nm according to the image; 4) Selective Μ 6 〇υ and 160 ° C temperature for exposure after exposure; and (5) K-solvent or Μ-alkaline imaging agent aqueous solution. Preferably, wherein the illumination according to the image is a monochromatic or multi-color source, the illumination is performed with a wavelength ranging from 1 90 to 450 nm, in particular from 1 90 to 2 60 nm. - Line · The photoresist of the present invention has a silly lithographic property* depending on the image illumination, particularly high sensitivity and high light transparency. Ministry of Economic Affairs Intellectual Property Office Employees Consumption Cooperative Printed The composition of the composition of the present invention is applicable as follows: a photoresist used as an electronic component, such as an etch resist, a plating resist or a solder resist, for manufacturing a laminated circuit A plate or thin film transistor resistive (TFT); used in the manufacture of printed circuit boards such as lithographic or screen printing plates for etching of molded articles, or for stereolithography or laser photography. The coated sheets and processing conditions can vary with the conditions. The compositions of the present invention are also particularly suitable as coating compositions for all types of substrates, including wood, fabric, paper, ceramic, glass, plastic, polyester, polyparaben, polyolefin or fiber acetate. Ester* especially thin-8 2 - This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1292851 A7 B7 V. Invention Description (called) Membrane type Plastic, but also particularly suitable for coating gold iridium, like N i , F e , Zn, Mg, Co or especially Cu and A 1 , also including S i ' lanthanum chloride or nitrite, on which M Imagewise illuminating an image. The invention also relates to the use of a compound of formula Ib, IIb or IIIb under acid action to produce a cross-linking composition as a photolatent acid supply, and/or in acid The use of a composition that increases the solubility under the action as a dissolution enhancer. Further subject matter of the invention relates to a method of crosslinking a compound capable of crosslinking under the action of an acid, the method comprising adding a compound of the formula lb, I lb, and/or II lb to the compound, and depending on the image or The light source of the K-wavelength of 1 50 - 1 500 nm is illuminated throughout the region. The invention also relates to the preparation of surface coatings, mime inks, printing plates, dental compositions, color filters, photoresists or image recording materials, or images for holographic photography, of formula I b, II b or III b Use as a light sensitive acid supply when recording materials, and for preparing surface coatings, mime inks, printing plates, dental compositions, color filters, photoresists or image recording materials, or for holographic photography A method of recording a substance by an image. The subject matter of the present invention is also directed to the use of a compound of formula I, I I or I I I as a photo-sensitive acid supply when preparing a color filter or a chemical-release photoresist. As described above, in the photocrosslinkable composition, an anthracene derivative is used as a latent catalyst: when it is irradiated by a light, it releases a catalytic crosslinking reaction. 83. The paper scale applies to the Chinese national standard ( CNS) A4 specification (210 X 297 public love ^ ~

1295281 Α7 Β7 V. Invention description uo acid. In addition to this, the acid released by the illumination can, for example, catalyze the removal of a suitable acid-sensitive protecting group from the polymer structure or the cleavage of the polymer containing the acid-sensitive group in the polymer backbone. Other applications are, for example, a color change system based on a Kp enthalpy change, or the solubility of a pigment protected by an acid sensitive protecting group. The anthracene derivative of the present invention changes the color of the pigment as the value of ρ Η changes - when used, it can also be used to produce a printed "print-out" image, as described in Japanese Patent Application JPH ei 4 , 3 2 8 5 5 2 - A or US 5 2 3 7 0 5 9 . These color change systems can also be used to monitor substances that are sensitive to heat or radiation in accordance with EP-1959. In addition to color change, it is also possible to precipitate pigments when acid-catalyzed to protect soluble dye molecules (as described in EP- 6 48 7 70 , EP-6 488 1 7 and EP- 7 4 2 2 5 5 ). The crystals thus can be used to produce a color filter as described in EP-654711 when the color of the latent pigment precursor is different in the color of the precipitated pigment crystal, or to print the image and serve as an indicator. . Compositions using Η 戚 戚 sensitive dyes or latent pigments and hydrazine derivatives can be used as indicators of electromagnetic radiation, such as 7-rays, electron beams, UV- or visible light, or simple disposable dosimeters. The dosimeter is advantageous. Finally, the hydrazine derivative in the aqueous solution of the almost insoluble alkaline developer can be converted into a free acid by light-introduction to make it soluble, and as a result, it can be dissolved when used together with a film-forming resin. Lifting agent. A resin capable of crosslinking under the action of an acid, that is, by the formula I, -8 4 of the present invention - the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) --------- ----装--- (Please read the note on the back to write this page) . -丨线· Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing can make it possible to reverse the contraction, consolidate I Specially urged in acid. The alcoholic acid is suspected to be agglomerated or the aldehyde is condensed. The acetaldehyde is condensed as water. 1295281 A7 ___B7 _____ V. INSTRUCTIONS (21) Examples of II or III photolatent acids, especially those which are crosslinked by the compound of formula I b, II b or III b are polyfunctional alcohols or hydroxy-containing acrylics and polyesters. A mixture of resins, or a partially acid-hardenable resin having an acetal functional derivative is generally any resin whose hardening can be accelerated by an acid catalyst, such as an am inop lasts or a phenolic resin. These resins are especially melamine, urea, epoxy, phenol, acrylic, polyester and alkyd resins, especially mixtures of acrylic, polyester or alkyd resins. Also included are modified surface coating resins* like acrylic modified polyesters and alkyd resins. Examples of various types of resins are acrylics, polyesters and alkyds, as described in Wagner, Sarx/Lackkunstharze (Munich, 1971), pages 86 to 123 and 2 2 9 to 2 3 8 , or

Ulliaann/Encyclopedia of Industrial Chemistry, Verlag Chemie, 1991, Vol. 18, 360 ff. Vol. A19, 371 ff 此 In the application of the surface coating, the surface coating preferably comprises an amine resin. Examples thereof are etherified or non-etherified melamine, urea, or hydrazine, biuret resin. Acid catalysts are particularly important when hardening surface coatings containing etherified amine based resins, such as methylated or butylated melamine resins (N-methoxymethyl- or N-butoxymethyl- Melamine) or methylated/butylated guanidine. Examples of other resin compositions are polyfunctional alcohols or hydroxy-based papers. The Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applicable (please read the following notes on the back page) ----- ---Book·丨丨I!丨·· . Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 B7 !295281 i, invention description () mixture of acrylic and polyester resin, or with polyfunctional dihydropropane Part of the derivative is hydrolyzed with polyvinyl acetate or polyvinyl alcohol, such as a derivative of 3,4-dihydro-2-pyridin-2-carboxycarboxylic acid. The polyoxyalkylene can also be crosslinked by an acid catalyst. These decane group-containing resins can be, for example, self-condensed by acid-catalyzed hydrolysis or crosslinked with a second resin component. An example of the second resin component is a partially hydrolyzed polyvinyl acetal or polyvinyl alcohol. This type of polycondensed polydecane oxygen is described, for example, in J.J. Lebrun, Η.P ode , Comprehensive Polymer Science, V o 1. δ , p 5 9 3 ,

Pergamon Press, Oxfod, 1989. Other cationizable polymerizable materials suitable for the preparation of surface coatings are ethylene-containing unplanar and compounds which can be polymerized by cationic reaction mechanisms, such as vinyl ethers, such as methyl vinyl ether, isobutyl vinyl ether, trimethylolpropane Vinyl ether, ethylene glycol divinyl ether; cyclic vinyl ethers, such as 3,4 dihydrogen-2-methylformamide-2H-pyran (dipolymerized acrolein) or 2-hydroxymethyl- 3*4-two 3,4-dihydro-2H-pyran-2-carboxylate of hydrogen-2H-pyran; vinyl esters such as ethylene acetate and ethylene stearate, mono- and di-olefins, like c (Methylstyrene, N-vinylpyrrolidone or N-vinylcarbazole. For specific purposes*, a resin mixture having a monomer or oligomeric component containing a polymerizable unplanar and group may be used. These surface coatings are also The compound of formula I, II or III can be used for hardening. In these processes, a reactive polymerization initiator or a photoinitiator can be additionally used. The former, the polymerization of the unsaturated group is initiated at the time of heat treatment, and the latter is in UV. The polymerization reaction is initiated upon irradiation. -86** Paper Zhangji^[Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the note on the back to write this page) Installation Line - Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1295281 Α7 Β7 V. DESCRIPTION OF THE INVENTION (A) The present invention also relates to a composition comprising: (a) a compound which hardens under the action of an acid, or a compound whose solubility increases under the action of an acid; and (b) - used as a photosensitizing property The acid supply agent is at least one compound of the formula I b, II b or III b as described above. The amount of the compound of the formula I, II or III or I b, II b or III b added to the composition is from 0 · 1 Up to 30% by weight, for example from 0 ♦ 5 to 10% by weight, in particular from 1 to 5% by weight. According to the invention, the compounds of formula I, I b * II, II b, III or III b can It is used together with other photosensitizing acid supply compound (b 1), other photoinitiator (d), sensitizer (e) and/or additive (c). Suitable photo-sensitive acid supply compound (bl), sensitizer (e) and additive (c) are as described above. Ministry of Economics intellectual property Examples of other photoinitiators (d) printed by the Bureau of Staff Consumer Cooperatives are reactive light-based agents such as those of benzophenones, acetophenones, such as cc-hydroxycycloalkylphenyl hydrazine, Alkoxy acetophenone, α-hydroxy- or α-amino-p-benzophenone, 4-mono-indenyl-1,3-dioxane, benzamidine alkyl ether and biphenyl methyl adenine Ketones, monophosphonium oxides, bis-phosphonium oxides, or titans. Examples of other photoinitiators which are particularly suitable are: 1-(4-dodecylbenzylidene)-1-1-hydroxy-1. Methyl monoethane, 1 -(4-isopropylbenzhydrazide)-1-hydroxyl-1 methyl monoethane, 1 benzothymol-1 monohydroxy-1-methyl-ethane, 1 One [4 - (2-hydroxyethoxy) -87- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) A7 1295281 B7 ___ V. Description of invention (material) (Please read the back first Note: Please fill out this page again) Monobenzhydrazide]-1 Hydroxy-l-monomethyl-ethane, 1-[4-(acryloxyethoxyethoxy)benzophenone]-1 Base one 1 Monomethyl-ethane, diphenyl ketone, phenyl-l-hydroxy-cyclohexyl ketone' (4-morpholine_benzamide)-1,4-benzyl-1,4-dimethylamino-propanone, 1 Mono(3,4-dimethoxyphenyl)- 2-benzyl- 2-dimethylamino-butan-1-one, (4-methylthiobenzhydrazide)-1-methyl-one 1 monomorpholinyl-ethane, benzamidine dimethyl hydrazine, bis(cyclopentadienyl)-double (2,6-difluoro-3-pyridyl-phenyl) titanium, trimethyl Benzoquinone diphenylphosphine oxide, bis(2,6-dimethoxy-benzonitrile) printed by the Intellectual Property Office of the Ministry of Economic Affairs, a consumer cooperative, (2,4,4-dimethylamyl) A Tenghua Oxygen 'bis(2' 4 ,6-trimethyl benzamidine)- 2,4-dipentyloxyphenyl-phosphine oxide, or bis(2,4,6-trimethylbenzene) Formamidine) Phenyl-phosphonated oxygen. Other suitable other photoinitiators can be found in U.S. Patent 4,950,581, the 20th, 35th to 21st, 35th. Other examples are trihalogenated methyltriazine derivatives or hexaarylbisimidazole compounds. Further examples of other photoinitiators are borate compounds, as described, for example, in U S - 47 7 2530, EP - 77 5 706, GB - 2307474, GB 23 0 7473 and GB - 230 - 4472. The borate compound is preferably used in combination with an electron accepting compound such as a dye cation or a thiazolone derivative. Other examples of other photoinitiators are, for example, peroxide compounds such as benzamidine peroxide (other suitable peroxides are described in U.S. Patent No. 495,081, Item 19, lines 17-25), or幼-88- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) !295281 A7 ----B7__ V. Invention description (A ) Sub-light initiator, like aromatic 糸铳 or pin Salts, such as those described in u S Patent No. 4 9 50581, No. 18, No. 6 to 19 Orange, Line 10, or cyclopentadienyl-arylene-iron (II) a complex salt such as (ns-isopropylbenzene) (π 5 -cyclopentadienyl)-iron (II) hexafluorophosphate. The surface coating may be a solution or dispersion of the surface coating resin dissolved in an organic solvent or water, but it may also be solvent-free. Particularly advantageous are surface coatings having a low solvent content, so-called high solid surface coatings, and powder coating compositions. The surface coating used may be a clear varnish, such as a final coating varnish for multi-calorie coating in the automotive industry. They may also contain pigments and/or fillers, which may be inorganic or organic compounds, and metal powders for the final coating of metallic effects. The surface coating may also include a relatively small amount of specific additives conventionally used in surface coating techniques, such as flow modifiers, rheological agents, leveling agents, anti-foaming agents, bleaching agents, adhesion enhancers, light stabilizers. , antioxidants, or sensitizers. A UV absorber such as a hydroxyphenyl-benzotriazole, a hydroxyphenyl-benzophenone, a decyl oxalate or a hydroxyphenyl-s-triazine compound may be added to the composition of the present invention. As a light stabilizer. These compounds or mixtures thereof may or may not be added with sterically hindered amines (HALS). Examples of such UV absorbers and light stabilizers are: 1.2-(2z-hydroxyphenyl)-benzotriazole, like 2-(2, monohydroxy-5'-methylphenyl)-benzotriazole, 2 — (3', -89- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 public Chu ^ one (please read the back of the note first ^ write this page) set -------- --Line « Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1295281 Α7 Β7 V. Description of the Invention (5'-1-2 Untert-Butyl-Hydroxyphenyl)-Benzotriazole, 2 (5 y Uncle Butyl- 2'-hydroxyphenyl)benzotriazole, 2 - (2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)-benzotriazole , 2-(3, ,5'-di-tert-butyl- 2/monohydroxyphenyl)- 5-chloro-benzotriazole, 2-(3/-tert-butyl- 2'-hydroxy- 5'-methylphenyl)-5-chloro-benzotriazole, 2-(3'-sec-butyl- 5'-tert-butyl- 2, monohydroxyphenyl)-benzotriazole , 2 — (2'-hydroxy-4'-octyloxyphenyl)-benzotriazole, 2 — (3' > 5 / 1-2 untert-pentyl- 2'-hydroxyphenyl)benzotriazole, 2 - (3, , 5'-bis-(α,α-dimethylbenzyl)-2'-hydroxybenzene Benzo)-benzotriazole, 2-(3/-tert-butyl-butyl- 2^-hydroxy-5, mono(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3^-tert-butyl-one-[2-(2-ethylhexyloxy)-carbonylethyl]- 2/-hydroxyphenyl)-5-chloro-benzotriazole, 2 - (3/monotert-butyl- 2, monohydroxy-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2 — ( 3 / untert-butyl- 2 '-Hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-benzotriazole, 2-(3'-tert-butyl- 2, monohydroxy- 5'-(2-oxo-oxygen) Carboylethyl)phenyl)-benzotriazole, 2-(3/-tert-butyl-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxybenzene Benzo)-benzotriazole, 2-(3'-dodecyl- 2'-hydroxy-5'-methylphenyl)-benzotriazole and 2 -90- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -------------- Packing - (Please read the back note first to write this page ) ->0. i line. Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1295281 Α7 Β7 5, invention description (magic) - (3 unter-butyl- 2'-------- Oxygen (please read the precautions on the back and fill out this page) Mixture of carbonylcarbonyl)phenyl-benzotriazole, 2,2'-methylene a pair [4,1,1,3,3— Tetramethylbutyl)-6-benzotriazol-2-ylphenol]; 2-[3, 1-tert-butyl- 5'-(2-methoxycarbonylethyl)- 2'-hydroxy- a lactide product of phenyl]-benzotriazole and polyethylene glycol 300; [R-CH2CH2-C 〇〇(CH2) 3 ] 2 — wherein R = 3'-tert-butyl- 4-, one Hydroxy-5, 2H-benzotriazole-2-phenyl-phenyl. 2 ♦ 2-hydroxybenzophenone, such as 4-hydroxyl, 4-methoxy, 4-octyloxy, 4-oxoanthracene, 4-dodecyloxy, 4-monobenzyloxy, 4, 2', 4, " trihydroxy or 2'-hydroxy-, 4,4, monodimethoxy derivative. Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperatives, Printing 3 ♦ Unsubstituted or substituted benzoic acid esters, such as 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenylsalicylic acid Ester, benzhydrin resorcinol, bis(4-tert-butylbenzyl hydrazide) resorcinol, benzamidine resorcinol, 3,5-di-tert-butyl- 4-hydroxyl 2,4-di-tert-butyl phenyl benzoate, cetyl 3,5-di-tert-butyl- 4-hydroxybenzoate, 3,5-di-tert-butyl- 4 Monohydroxyl octadecyl benzoate, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2-methyl 4,6-di-tert-butylphenyl ester. 4 ♦Acrylate, such as α-cyano-anthracene, ethyl 2-diphenylacrylate, or isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester, α-cyano-1/3. Base-Ρ-methoxy-cinnamic acid methyl ester, or butyl ester, α-91- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 _B7____ V. Description of invention ( β ) monocarbomethoxy-P-methoxy-cinnamic acid methyl ester, N — (/3 —carbomethoxy-fluorenylvinyl)-2-methyl-indene. (Please read the notes on the back and fill out this page) 5 ♦ Stereo hindered amines, like bis(2,2,6,6-tetramethyl-piperidinyl)sebacate, double (2,2, 6,6-tetramethyl-pyridinyl) succinate, bis(1,2,2,6,6-pentamethylpiperidinyl)sebacate, n-butyl-3,5-di Mono-tert-butyl- 4-hydroxybenzyl-malonate bis(1,2,2,6,6-pentamethylcyclohexyl)ester, 1 monohydroxy-2,2,6,6-tetramethyl a condensed product of hydroxy-p-hydroxypiperidine and succinic acid, hydrazine, Ν'-bis(2,2,6,6-tetramethyl-tetra-piperidyl)hexamethylenediamine and 4-tert-octyl A condensed product of a 2,6-dichloro-1,3,5-s-trisyl group, a tris(2,2,6,6-tetramethyl- 4-pyridyl)zinc-triacetic acid Ester, tetrakis(2,2,6,6-tetramethyl-tetra-piperidinyl)- 1,2,3,4-butane tetracarboxylate, 1, 1 (1,2-ethanediyl) A pair of (3,3,5,5-tetramethyl-pyrazinone), 4-benzoic acid-2,2,6,6-tetramethylcyclopyridine, 4-stearyloxy- 2 , 2,6,6 - tetraseptylpiperidine, double (1,2,2,6,6 - five-five Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed piperidine) 2- 2 - n-butyl one 2 —(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-three丫 〔 [4 ♦ 5] 癸 一 2 2,4 1-2 ketone, bis (1 octyloxy-2,2,6,6-tetramethylpiperidinyl) sebacate, double (1 xin Oxygen-2,2,6,6-tetramethylpiperidinyl) succinate, hydrazine, Ν'-bis (2,2,6, -92- This paper scale applies to China National Standard (CNS) A4 Specifications (210 X 297 mm) I29528l

V. Description of invention (η) (Please read the note on the back and then fill out this page) 6>Team-methyl-4.1-steep base) Rokko and 4-morpholino-2, S~2N-1 ' 3 ' 5 - 嚷 condensed product ' 2 - chloro- 4, 6-di (4-n-butylamino- 2,2,6,6-tetramethylpiperidinyl)-1,3, a condensation product of 5-triazine and 1,2-bis(3-aminopropylamino)ethane, 2-chloro-4,6-di(4-n-butylamino)- 1,2,2 a condensation product of 6,6-pentamethylindenyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, 8-ethylidene-3 —12 烧基一7 ' 7 ' 9 ' 9 —Tetramethyl- 1 ,3,8 —Three η 丫 〔 [4· 5]癸焼一2,4 一二嗣,3—12焼基一1 mono(2,2,6,6-tetramethyl-tetra-piperidinyl)pyrrolidine-2,5-dione, 3-dodecyl-l-one (1,2,2,6,6 - pentamethyl- 4 -piperidinyl)-pyridyl-only 2,5-dione. 6 ♦ Diammonium oxalate, like 4,4'-dioctyloxy-oxalyl aniline, 2, 2'-diethoxy-oxalyl aniline, 2,2' - Eryi Xin Economic Department Intellectual Property Bureau employee consumption cooperative printed oxy-5,5'-di-tert-butyl-butyl-oxalyl aniline, 2,2, one or two (twelten alkoxy)-5,5'-two uncle Butyl-p-oxalyl aniline, 2-ethoxy- 2'-ethyl-doxaphene aniline, Ν,! ^' A pair of (3-dimethylaminoaminopropyl) ethanediamine, 2-ethoxy-5-tert-butyl- 2'-ethyl oxalic acid, and 2 a mixture of ethoxy- 2'-ethyl-5,4'-di-tert-butylacetophenone, hydrazine- and ρ-methoxy-, and hydrazine- and hydrazine-ethoxy-di- A mixture of substituted oxalicin and aniline. -9 3- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 B7 V. Invention description (w) 7 · 2 — (2 — Hydroxyphenyl)-1,3,5-triazine' like 2' 4,6-tris(2-hydroxy-4-isooctyloxyphenyl)-1,3'5-pyridazine, 2 — (2 — Hydroxy- 4-octyloxyphenyl)- 4'6-bis(2,4-dimethylphenyl)- 1,3,5-triazine, 2-(2,4-dihydroxyphenyl) a 4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-double (2-amino- 4-propoxyphenyl)-6-( 2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-isooctyloxyphenyl)- 4'-6-bis(4-methylphenyl)- 1,3,5-triazine, 2 - (2~hydroxy-1,4-dodecyloxyphenyl)- 4,6-bis(2,4-dimethylphenyl)-1,3,5 — Triazine, 2 - [2 - thiol 4-(2-hydroxy-3-methoxy-propoxy)phenyl]- 4 6-bis(2-dimethylphenyl)-i, 3,5-triazine, 2-(2-hydroxy-4-iso(2-hydroxy-3-methoxy-propoxy)phenyl]- 4,6-bis(2,4-dimethylphenyl)- 1,3,5-triazine, 2 —[4-dodecyl-tridecyl-oxy-(2-hydroxypropyl) Alkyloxy-2-hydroxyl-phenyl]- 4,6-bis(2,4-monomethylphenyl)-1,3,5-triazine. 8 · Phosphites and phosphonites such as triphenylphosphite, diphenylphosphonium phosphite, phenyl dialkyl phosphite, tris(nonylphenyl) discate, three Lauryl phosphite, tris(octadecyl)phosphite, distearyl-pentaerythritol di squarate, tris(2,41-2 di-tert-butylphenyl) phosphite, Diisodecylpentaerythritol diphosphite, double (-94- This paper scale applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) H 11 n 1B1 a — nn tmmmm ΛΜΙ n 0 I an 1« n ϋ 11 mmmme 1 ·ϋ 1 in em- tat n I line #. (Please read the notes on the back and fill out this page) 1295281 A7 B7 V. Invention description (V) 2,4 One or two uncle Butyl phenyl) pentaerythritol diphosphite, double ((Please read the back note for this page) 2,6 —di-tert-butyl- 4-methylphenyl)pentaerythritol diphosphite, double Isoisodecyloxy-pentaerythritol diphosphite, bis(2,4,2-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, double one (2,4,6 — Tris-tert-butylphenyl)pentaerythritol diphosphite, tristearyl-sorbitol triphosphite, tetrakis(2,41-2 di-tert-butylphenyl)-4,4'-biphenyl Diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl- 12H-dibenzo[d · g]-1,3,2-dioxaphosphorus Phosphonine, 6-fluoro-2,4,8,10-tetra-tert-butyl- 12-methyl-dibenzo[d,g]-1,3,2-dioxaphosphine , bis(2,4,2-di-tert-butyl-6-methylphenyl)methylphosphite, bis(2,4,2-di-tert-butyl-6-methylphenyl)ethyl Phosphate ester. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperatives. These light stabilizers can be added, for example, to adjacent surface coating materials, and then slowly dispersed into the protected squeezing lacquer. The adjacent surface coating layer can be the starting layer under the baking varnish or the final coating varnish on the baking varnish. It is also possible to add to the composition, such as a photo-sensitive agent, which can change or increase the photosensitivity, such that the light irradiation time can be reduced, and/or other light sources can be used. Examples of photo-sensitizers are aromatic quinones, or aromatic furfural compounds (such as the compounds described in US 4 0 1 7 6 5 2), 3-mercapto-monofonoids (as described, for example, US 4366) 2 -95- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) "" 82 592 A7j V. Invention description (bamboo) • II I------—I! ti Layer I (please read the note on the back to write this page) 28, EP - 738928, EP-22188), keto-coumarin (as described in US - 44346 '3 3 , EP - 538 997, JP8 2 72095 — A), styryl- ruthenium (as described in EP-624580), 3-(arylmercapto) thioporphyrin, thioxanthones, condensed aromatic compounds, like perylene Benzene, an aromatic amine (as described, for example, in US-406 954 or W096/4 1 237) or a cationic or basic coloring agent (described in, for example, US-4 0 2 607), such as blush ( Eosine), Rhodamine and Erythroin stains, and dyes and pigments, as described in JP8320551 - A, EP-747771, JP - 7036179 - A, EP - 619520, JP -6161109-A JP604 3641, JP_ -- Line · Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed 6 035198-A, W093/15440, EP56 8993, JP5005005 - A, JP-50274 32 - A, JP - 5301910 - A, JP - 4014 083 - A, JP - 4294148 - A, EP - 359 431, EP - 103294, US - 4282309, EP-390 2 5, EP - 5274, EP - 72771 3, EP - 726497 or DE 20274 6 7. Other conventional additives are, depending on the purpose, optical brighteners, fillers, pigments, such as latent pigments, dyes, colorants, wetting or flow improvers and adhesion promoters. When hardening thick and dyed coatings, add fine glass beads or powder-96- This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 Α7 Β7 V. Invention description (u) Glass Dimensions (as described in US - 5 0 1 3 7 6 8) may also be suitable. Examples of other photoinitiators or additives have been previously described. (Please read the notes on the back and fill out this page.) Deuterium derivatives can also be used, for example in hybrid systems. These systems are based on formulations that are sufficiently hardened by two different reaction mechanisms; examples of which include systems capable of producing acid-catalyzed crosslinking or polymerization components, but also other components that can be crosslinked by a second reaction mechanism. An example of the second reaction mechanism is a cross-linking reaction of a radical full cure, an oxidative crosslinking or a humidity-initiated crosslinking. This second hardening mechanism can also be initiated solely by heat, if desired, by the addition of a suitable catalyst, or by the use of a second photoinitiator. Suitable other photoinitiators are those as described above. If the composition comprises a reactive crosslinkable component, the hardening process, especially the dyed composition (eg, ruthenium dioxide dioxide), can be aided by the addition of a component that forms a reactive group under thermal conditions, like an azo compound. , for example, 2,-azobis(4-methoxy-2,4-dimethylpentanenitrile), triazene, diazo sulfide, pentadiene or peroxide, Ministry of Economic Affairs Intellectual Property Office employees Consumer cooperatives print images such as hydrogen peroxide or peroxide carbonates such as tert-butyl hydroperoxide as described, for example, in ΕΡ245639. The addition of an oxygenation initiator, like a cobalt salt, promotes the oxidation and crosslinking of the reaction by the aid of oxygen in the air. The surface coating can be applied by any of the methods known in the art, such as spraying, brushing or dipping. When using a suitable surface coating '-97· This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. Description of invention (training) Electrical properties, such as electrophoretic coating Cover is also possible. After drying, the surface coating is irradiated by calendering. This surface coating film can be sufficiently hardened by heat treatment if necessary. Compounds of formula I, I I or I I I can also be used in hardened mouldings made of the composite. This composite is made from a self-supporting parent material, such as glass enamel, impregnated calender hardenable formulation. From ΕΡ - 592 1 39, it is known that an anthracene derivative is used as an acid generator which is photoactivated in a composition suitable for surface treatment and cleaning of glass, aluminum and tantalum surfaces. The use of these compounds in this organic ruthenium system can result in compositions having significantly better storage ear characterization than those using only vaginal acid. Compounds of formula I, II and III are also suitable for this application. The anthracene derivative of the present invention can be used for a shaped polymer which is subjected to an acid-induced transition state to a state in which it is necessary to use a photolithography, for example, the anthracene derivative can be used as an emissive polymer. Pattern formation* as described in ML Renak; C. Bazan; D. Roi t man; Advanced materials 1997, 9, 392. This emissive polymer can be used to fabricate photomicrographs (L E D ) which can be used to fabricate displays or data storage media. The precursor of polyimine (such as a polyimine precursor having an acid labile protecting group which changes solubility in an imaging agent) can likewise be irradiated by radiation to form a patterned polyimide layer. Can be used as a protective coating for the manufacture of microchips and printed circuit boards, barrier layers and buffer layers -98- This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read first Precautions on the back side Fill in this page) Order---------Line· Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1295281 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed V. Invention Description uo 0 When this formulation is used to fabricate computer wafers and is used sequentially to stack printed circuit boards, stress buffer layers and insulating layers, it can also be used as conformal coatings, photoimageable dielectrics (photoimagable) Dielectric as ) ° Conjugated polymers * Methods like polyaniline proton proton stimuli, which are known to be converted from semiconducting to electrically conductive. The anthracene derivative of the present invention can also be used for an iaagewise irradiate composition containing the conjugated polymer, and the iridium is embedded in the insulating material (non-exposed area) to form a conductive structure (exposure region). The substance can be used as a wire or a connecting part for producing electronic components. A light source suitable for the composition comprising a compound of formula I, II or III is a radiation source having a wavelength of from about 150 to 1 500 * for example from 1 80 to 1 000, or preferably from 1 90 to 700 nm, Μ and e-beam And high-energy electromagnetic radiation, such as X-rays. Point light sources or flat light sources (light blankets) are suitable, examples are carbon arc lamps, xenon arc lamps, medium-pressure, high-pressure and low-pressure mercury lamps, and optional bismuth metal halide coating (metal one) Halogen lamp), microwave excited gold vapor lamp, excitation lamp (excimer), super actinic fluorescent lamp, fluorescent lamp, argon white hot lamp, electronic flash, photo floor lamp, electron beam and X-ray ( Generated by synchronous acceleration or laser plasma). The distance from the lamp to the exposed substrate of the present invention is, for example, from 2 cm to 150 cm, depending on the end use and the type and/or strength of the source. Therefore, a particularly suitable light source is mercury vapor lamp-99- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) ------------------ ---Order---------Line- (Please read the notes on the back and fill in this page) 1295281 Α7 Β7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperatives printed five, invention description (miao), especially It is a neutral high-pressure mercury lamp. If necessary, the K filter filters out different wavelengths of light emitted by the light source, especially short-wavelength rays. However, it is also possible to use a low-energy lamp (such as a fluorescent tube) capable of emitting a suitable wavelength, an example being a Philips TL03 lamp. Another type of light source is a light-emitting diode (LED) that emits different wavelengths throughout the spectral region, either as a small spectral band source or as a broad band source (white light). Suitable sources of illumination are, for example, excitation lasers, such as Kr-F lasers, wavelengths of 248 nm, Ar-F lasers, wavelengths of 93 nm or F2, and wavelengths of 1 5 7 n m. It is also possible to use a laser in the visible or infrared region. Particularly suitable are mercury i, h and g rays having wavelengths of 3 6 5 * 405 and 436. Suitable laser beam sources are, for example, argon ion lasers that emit light at wavelengths of 454, 458, 466, 472, 478, 488 and 514 nm. Nd-YAG lasers with a wavelength of 1 064 nm and their second and third high-modulation waves (532 nm and 355 nm, respectively) can also be used. Also suitable are, for example, helium/cadmium lasers having a wavelength of 4 4 2 n m or lasers in the U V region. When using this type of ray, it is not absolutely necessary to use a reticle and photopolymerization coated contact Μ to produce a positive or negative photoresist; the controlled laser beam can be written directly onto the coating. For this reason, the high-sensitivity substance of the present invention is very advantageous, and can be written at a relatively high speed with a relatively low energy. When irradiated, the anthracene derivative of the composition in the irradiation area of the surface coating is decomposed to form an acid. Compared with the traditional high-intensity ray UV hardening of the present invention, the present invention-100- this paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -------------- ----------Book--------Line· (Please read the note on the back and fill in this page) 1295281 Α7 Β7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention The activation of the illustration (吣) can be carried out with relatively low intensity radiation, including daylight (sunlight), and a light source equivalent to daylight. Daylight is different in the spectral composition and intensity from the conventional U V artificial light source. The absorption characteristics of the compounds of the invention are also suitable for use with daylight as a natural source of radiation hardening. An artificial light source that can be used to activate the compound of the present invention, which is equivalent to daylight, is a low intensity projection lamp, such as a specific fluorescent lamp, such as a P h i 1 i P s T L G 5 special fluorescent lamp, or a Philips TLQ9 special fluorescent lamp. Lamps or daylight with high daylight content are themselves particularly capable of hardening surface coatings in a tack-free manner. In this case, an expensive hardening device is superfluous, and this composition can be used especially for exterior coatings. K Daylight or Baidang's light source hardening in sunlight is an energy-saving method that prevents volatile organic components from escaping from the external environment. For the conveyor belt method suitable for flat objects, it is also possible to use sunlight as an external coating hardening for stationary or fixed objects or structures. The surface coating to be hardened can be directly exposed to sunlight or a light source equivalent to sunlight, however, this hardening can also occur after a transparent layer (e.g., after a layer of glass or plastic). The invention will be more fully described in the following examples, and in the remainder of the specification and the scope of the claims that follow, unless otherwise specified, the parts and percentages are calculated by weight. When the alkyl group used contains more than one carbon atom, it means a normal isomer 0 without specifically indicating the isomer. Example 1: 2,2,2-trifluoro-1-phenyl-B Ketone 肟0-0-A-101- (Please read the notes on the back first ν装·i_ 1 Write this page) Order: Line: This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. INSTRUCTIONS (0) Base sulfonate 1 ♦ 1 : 2,2,2 —trifluoro- 1 benzophenone-ethanone oxime 2 5 g (0 · 1 4 4 mol) of 2,2 2, trifluoro- 1 phenyl ethyl ketone was dissolved in 40 ml of ethyl ketone under 8 Ο 。. K droplets are added to this solution by adding 1 0 ♦ 5 g (〇·1 5 1 mol) of hydroxyammonium chloride dissolved in 20 ml of water and 2 0 ♦ 1 g (〇· 2 4 5 mol a solution of sodium acetate, refluxing the mixture overnight, and distilling off the solvent in a rotary evaporator, the residue is poured into water, the white precipitate is washed with water, and dried under vacuum to obtain 24, 4 g of 2, 2, 2 Trifluoro-1-1-phenyl-ethanone oxime. The crude product was taken directly to the next step without purification. 1 · 2 : 2,2,2 -trifluoro-1-1-phenyl-ethanone oxime- 0-methanesulfonate 2 · 0 g (10 · 6 mmol) of 2,2,2-trifluoro The 1-phenyl-ethyl ketone oxime was dissolved in 40 ml of tetrahydrofuran (THF) and cooled in an ice bath. To this solution was added 1,3 g (1 1 ♦ 7 mM) of methylsulfonium chloride, followed by hydrazine dropwise addition of 1 ♦ 6 g (15,9 mmol) of triethylamine. The reaction mixture was stirred at 0 ° C for 5 hours, poured into ice water and extracted with ethyl acetate. The organic phase was washed with water and brine, dried (M g S 0 4 ) and concentrated. The residue was purified by repeated precipitation with methanol and water to obtain 2 · 3 g (8 · 6 mmol; 8 1. %) of 2,2,2-trifluoro-l-phenyl-ethyl-anthracene — (Methyl sulfonate) * It is a white solid, melting point (m · p ·) -102- The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the back note first) Matters re-filled on this page) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed Economy Ministry Intellectual Property Bureau Staff Consumer Cooperatives Printed 1295851 Β7 V. Invention Description (call) 5 1 — 6 4 °C. The structure is determined by the spectrum of 1 Η - N M R: (C D C 1 3 ) δ [ppm] : 3 * 2 6 (s, 3H), 7. 4 7 - 7 . 6 3 ( m , 5 Η ). Example 2: 2,2,2-trifluoro- 1 phenyl-ethyl hydrazine- 1 (1 0 - camphor oxime sulfonate) 2 * 0 g (1 〇 · 6 mmol) 2, 2,2-Trifluoro- 1 phenyl-ethyl hydrazide (prepared in Example 1:1) was dissolved in 40 mL of THF and cooled in an ice bath. 2 ♦ 9 g (1) was added to the solution. 1 · 6 millimoles of 10 - camphor sulfonium chloride, followed by droplets of 1,6 grams (15 ♦ 9 millimoles) of triethylamine. The reaction mixture was stirred at ◦ 2 for 2 hours and poured into ice water to dry (MgSO S 4 ) and concentrated. The residue was purified by flash chromatography on silica gel. The eluting solvent was ethyl acetate and hexane (1:9) to give 2,2 g (5 ♦ 5 mM; 52%) of 2, 2, 2 -Trifluoro-1-1-phenyl-ethanone oxime-(10-camphorin sulfonate), which is a pale yellow liquid, the structure is confirmed by 1 Η-NMR spectrum (CDC13), d [ppm]*: Ο · 92 ( s,3H) ,1 * 14 ( Z ) /1.18 (E) (s,3H) ,1,40 - 1·50( m,lH) ,1,66—1·75(ιη,1Η) , 1'92 — 2·19(γπ,3Η) , 2·3 4—2·5 5 (ιη, 2Η), 3·28(Ε)/3·33(Ζ) (d, 1 Η ) , 3 ·87(Ζ)/3·97(Ε) (d,lH) -103- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill in the form) Page) Order---------Line - 1295281 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed Β7 Β7 V. Invention description (π), 7·48 — 7·65 (πι, 5Η). The 11^1111 spectrum reveals that the product is a mixture of ruthenium and osmium isomers (9 i 1). The absorption signals are divided into E- and Z-configurations. Example 3: 2' 2' 2 -trifluoro- 1 -phenyl-ethyl hydrazine g-b-one (4-methoxyphenyl sulfonate) 2.0 g (10.6 mmol) of 2,2,2 Trifluoro-l-phenyl-ethanone oxime (prepared in Example 1-1) was dissolved in 40 ml of THF and cooled in an ice bath. To this solution was added 2 · 4 g ( 1 1 · 7 mmol) of 4-methoxyphenylsulfonium chloride, followed by droplets of 1 ♦ 6 g (1 5 · 9 mmol) The triethylamine was stirred at 0 t for 5 hours, poured into ice water and extracted with ethyl acetate. The organic phase was washed with water and brine, dried (M g S 0 4) and concentrated. The residue is recrystallized from methanol to give 2 · 3 g (6 ♦ 5 mM, 61%) of 2,2,2-trifluoro- 1 phenyl-ethyl hydrazine- 0 - (4 A Oxyphenyl sulfonate), which is a white solid, m ♦ p · 6 9 - 7 3 °C. Structure and 1 Η — ! Si M R spectrum correspondence ( C D C 1 3 ) : S[ p p m]: 3 ♦ 9 2 ( s, 3 Η ),

7·05 ( d · 2 Η ) , 7·3 8 - 7·58 (m, 5H ), 7·95 (d, 2H) 〇 Example 4 : 2, 2, 2 —trifluoro- 1 -phenyl- Ethyl ketone oxime 0 - (1 - naphthyl sulfonate) -104- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) ------------- --------Book --------- Line · (Please read the note on the back and fill in this page) 1295281 A7 B7 V. Invention Description ('°\) 2 ♦ 0g ( 1 2·6 mmoles of 2,2,2-trifluoro- 1 phenyl-ethyl ketone oxime (prepared in Example 1 ♦ 1) is dissolved in 4 〇 ml (please read the notes on the back and fill in the form) Page) Ding HF, and the ice bath is cooled. Add 2 · 6 g (1 1 · 6 mmol) of 1 -Craft sulfonium chloride to the solution, followed by droplets

1 ♦ 6 g (1 5 ♦ 9 mmol) of triethylamine was added, and the reaction mixture was stirred at 0 ° C for 4 hours, poured into ice water and extracted with ethyl acetate. The organic phase was washed with water and brine, dried (N1 g S 0 4 ) and concentrated. The residue is recrystallized from acetone and water to give 3 · 7 g (9 ♦ 8 mmol, 92%) of 2,2,2-trifluoro-1-phenyl-ethyl-indole- 0- (1 Naphthyl sulfonate), which is a white solid, γπ·ρ, 96 - 104 °C. The structure is consistent with 1 Η NMR spectrum (CDC 1 3 ) : δ [ppm] : 7·23 - 7·38 ( m, 2H) , 7·43 - 7·85 (m, 6H), 7·95 - 8 · 05 (γπ, 1Η), 8, 18 - 8·27 (m, lH), 8. 37-8·83 (τη, 2Η). Example 5: 2,2,2-trifluoro-1-phenyl-ethyl ketone oxime — (Printed by the Ministry of Economic Intelligence, Employees' Consumer Cooperatives, 2-naphthyl sulfonate) 2 ♦ 0 g (1 0 ♦ 6 millimoles of 2,2,2-trifluoro-l-phenyl-ethanone oxime (prepared in Example 1 ♦ 1) was dissolved in 40 mL of THF and cooled in an ice bath. 2 ♦ 6 g (1 1 ♦ 6 mmol) of 2-naphthylsulfonium chloride was added to the solution, followed by

Add 1 · 6 g (1 5 · 9 mmol) of triethylamine at 0 °C -105- This paper scale applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1295281 Ministry of Economics wisdom The property bureau employee consumption cooperative printed A7 B7 V. Inventive Note (丨.X) The reaction mixture was stirred for 4 hours, poured into ice water, and extracted with ethyl acetate. The organic phase was washed with water and brine, dried (M g S 0 4 ) and concentrated. The residue is recrystallized from methanol to give 2 ♦ 8 g (7.4 g, 70%) of 2,2,2-trifluoro-l-phenyl-ethanone oxime-0-(2-naphthalene Base sulfonate), which is a white solid, m· ρ · 1 17 -1 20 °C. The structure is consistent with 1 Η-NMR spectrum (CDC 1 3 ): δ [ppm]: 7·37-7·58 (γπ, 5Η), 7,64-7,78 (m, 2H), 7.92 - 8 ·〇9 (m, 4H), 8·63 (s, lH). Example 6: 2,2,2 -trifluoro-l-phenyl-e-ketoneoxime- 0 (2,4,6-trimethylphenylsulfonate) 2·0 g (10.6 mmol) 2,2,2-Trifluoro-l-phenyl-ethanone oxime (prepared in Example 1 ♦ 1) was dissolved in 40 mL of THF and cooled in an ice bath. 2 ♦ 5 g (1 1 · 6 mmol) of 2,4,6-trimethylphenylsulfonium chloride was added to the solution, followed by the addition of 1 ♦ 6 g (1 5 · 9 mmoles of triethylamine, the reaction mixture was stirred at 0 C for 4 hrs, poured into ice water and extracted with ethyl acetate. The organic phase was washed with water and brine, dried (MgSO4) and concentrated. The residue is recrystallized from methanol and water to give 3,2 g (8.66 mmol, 81%) of 2,2,2-trifluoro-l-indenyl-ethyl-indole- 0. 4,6-trimethylphenyl sulfonate), which is a white solid, mp· 90 — 10 3 1C, structure -106- This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the notes on the back and fill out this page)

1295281 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed A7 B7 V. Invention Description () and 1 Η - NMR Spectral Conformity (CDC 1 3 ) : d [ppm] : 2·34(Ε)/2·36 (Ζ) (s,3H), 2·60(Ζ)/2·68(Ε) (s,6H) ,7 ·〇(m,2H) ,7,40(s,2H) ,7·47 - 7.58 ( m , 3 Η ). The 1 H-NMR spectrum revealed that the product was a mixture of Z and E isomers (4:1). The absorption signal is divided into E- and Z-configurations. Example 7: 2,2,2-trifluoro-1,4-(4-methylphenyl)-ethyl-indole- 0-(10-camphor sulfonate) 7,1 : 2,2,2-trifluoro 1-1 (4-methylphenyl)-ethanone 50·0 g (0.543 mol) of toluene and 66,3 g (0 ♦ 543 mol) of 4-dimethylaminopyridinium in 700 ml Mix in C Η 2 C 1 2 and cool in an ice bath. In this solution, 1 14 ♦ 0 g (0 · 543 mol) of trifluoroacetic anhydride was added in the form of Κ droplets, followed by a portion of 1.7 g (1 ♦ 25 m). A 1 C 13 . The reaction mixture was stirred at room temperature overnight, poured into ice water and extracted with <RTI ID=0.0>> The residue was distilled at 90 ° C / 15 mmHg to give 49.5 g of the product as a colorless liquid. 7. 2:2,2,2—Trifluoro-1(4-methylphenyl)-B-1 0 7 - This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) - --------------------- Order --------- Line · (Please read the notes on the back and fill out this page) 1295281 A7 B7

V. Description of invention) Printed by the Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative _肟49 · 5 g (0 ♦ 263 mol) of 2,2,2-trifluoro-(4-methylphenyl)-ethanone In 250 ml of ethanol (8 〇 ° C), in the solution of the K, the droplets of K are added to 1 9 ♦ 2 g (0 · 27 6 mol) of ammonium hydroxyammonium dissolved in 1 2 5 ml of water. Chloride and 36 ♦ 7 g (0 · 44 7 mol) of sodium acetate, reflux reaction mixture 3 * 5 hours ' Η @ @ 丨 丨 丨 丨 倒 ' ' ' 冰 冰 胃 胃 胃 胃 胃After filtration, 39 ♦ 2 g of 2,2,2-trifluoro-1(4-methylphenyl)-ethanone oxime was obtained as a white solid, γπ·ρ· 54 - 68 °C. The crude product can be used directly in the next step without purification. 7.3 : 2,2,2 —trifluoro- 1 -(4-methylphenyl)-ethanone oxime- 0 - (1 0 - camphorquinone sulfonate) 3 ♦ 0 g (14 · 8 mmol) The 2,2,2-trifluoro-l-(4-methylphenyl)-ethanone oxime was dissolved in 30 ml of THF and cooled in an ice bath. 4 ♦ 1 g (1 6 · 2 mmol) of 10 - camphor sulfonium chloride was added to the solution, followed by K droplets to add 2 · 3 g (2 2 · 2 mmol) Triethylamine. The reaction mixture was stirred at 0 ° C for 90 minutes, poured into ice water and ethyl acetate. The organic phase was washed with water and brine, dried (MgSO4) and concentrated. The residue was purified by flash chromatography on silica gel. The eluent was ethyl acetate and hexane (1:9) to obtain 3,2 g (7·7 mmol; 52%) of 2, 2, 2 - Trifluoro-1(4-methylphenyl)-ethanone oxime-0 0-1 0 8 - This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) ------- ------Install ---1 (Please read the note on the back to write this page) Order --- ; Line · 1295281

Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperatives, Printing, V. Inventions (, 〇~(1 〇-樟 醯 醯 sulfonate), which is a colorless liquid. The structure is consistent with 1H-NMR spectrum (CDC13): d [ppm] : ◦•92(s,3H) ,1·14(Ζ)/1·18(Ε )(s,3H) ,:L,42 - l,50(m,lH), 1 *64-1 *74 (m* 1H) ,1·93 — 2·18 (m,3H) , 2·35 - 2·56 (m,5H), 3·28(Ε)/3·33(Ζ) (d,lH) , 3*87 (Ζ) / 3*94 (Ε) (d,lH), ?·27 - 7·32(τη,2Η) , 7·43(Ζ)/ 7·53(Ε) (d,2H 〇1 Η — NMR spectroscopy reveals that the product is a mixture of ruthenium and osmium isomers (4:1). The absorption signal is divided into Ε- and Ζ-configurations. Example 8: 2, 2, 2 - trifluoro-1 4 monomethylphenyl)-copper oxime-0-(methanesulfonate) 3 ♦ 0 g (1 4 ♦ 8 mmol) of 2,2,2-trifluoro-1 (4 A) Phenyl phenyl) monoethyl ketone oxime (prepared in Example 7.2) was dissolved in 30 ml of THF and cooled in an ice bath. 1.9 g (16 * 2 mmol) of methyl was added to the solution. Sulfonium chloride, followed by Κ droplets, added 2 · 3 grams 22 ♦ 2 mmol of triethylamine. The reaction mixture was stirred at 0 Torr for 4 hours, poured into ice water and extracted with ethyl acetate. The organic phase was washed with water and brine, dried (M s S 0 4 ) and Concentrate. Residue Κ flash chromatography on gelatin, the eluent is ethyl acetate-109- This paper scale is applicable to China National Standard (CNS) A4 specification (210 x 297 mm) (please read the notes on the back first) Write this page)

-n ϋ n I i^in · _1 fli ϋ _1· · ϋ n I « 1295281 A7 B7 V. Description of invention (―) Ester and hexane (1 5 : 8 5 ), available 2 ♦ 6 g (9 ♦ 2 Millol; 6 2 %) 2,2,2-trifluoro-l-(4-methylphenyl)-ethanone oxime-Q-(methylsulfonate), which is a colorless solid. m ♦ p ♦ 56 — Structure of 67°C conforms to 1 H — NMR spectrum (CDC 1 3 ) : δ [PPm]: 2 ♦ 4 2 ( s , 3 Η ) , 3*27(s, 3H) , 7.26 - 7·53 (γπ, 4 Η ). Example 9: 2,2,2-trifluoro-1(2-methylphenyl)-ethanone 8 bow- 0 — (1 0 - camphor sulphate) 9· 1 : 2, 2, 2— Trifluoro-l-(2-methylphenyl)-ethylm consists of 25, gram (0.146 m) of 2-brominated toluene and 4 ·3 g (〇♦ 175 m) of magnesium at 100 The Griguard reagent was prepared in milliliters of diethyl ether in the form of a K droplet. The Grignard reagent was added to a solution containing 22 x 8 g (0.11 mol) of ethyl trifluoroacetate dissolved in 1 2 0 In a solution of ml of diethyl ether (temperature of 178 ° C), the temperature of the reaction mixture was allowed to rise to room temperature, and stirred for further 1 hour. 300 ml of an aqueous solution of N Η 4 C 1 and 1 ml of 1 NHC 1 were added to the mixture, the aqueous phase was removed, the organic celsium NH4Cl solution and brine were washed, dried (MgS 〇 4 ) and concentrated. Residue K flash chromatography was purified on tannin extract, and the eluting agent was hexane'. 6 ♦ 3 g of 2,2,2-trifluoro- 1 (2-methylbenzene-HO- paper scale applicable China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the notes on the back first)

--- II · Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1295281 A7 B7 V. Invention description (A) base) Ethyl ketone, which is colorless fatigue 9 ♦ 2 : 2,2 嗣肟 2 - trifluoro 1 one (2-methylphenyl)-ethylidene is 2 · 5 small saline 2, which is white 9 · ketone oxime (and Μ 3 · 7 (1 to 7 grams of 2 ~ 8 0 °0) Pour washing, 2,2 color solid grams (0 · methylphenyl, dissolved in 4 grams (0 ♦ 〇 3 into ice water 0 2 0) - in the liquid, 0 · 0 3 moles, and to Mo Ear) 嗣 dissolved in ethyl acetate (drops 2 0 mol) of ethyl acetate (MgS 〇 4) and 2, 20 mM of the ear) sodium hydroxylate, ester extraction concentrated, 2, 2 liters of B added to the solvent The ammonium chloride is stirred and reacted. The organic one can be obtained by adding 2-trifluoro- 1 -(2-methylphenyl)ethyltrifluoroalcohol, at a temperature of 10 milligrams and the mixture of the phase K water and ♦ 7 grams of _ 3 The crude product of the bow can be directly used in the next step without purification. 3:2,2,2 -trifluoro- 1 -(2-methylbenzene 0 - (1 0 - camphorquinone sulfonate) 9 m 2,2 ethyl hydrazine in Mohr) Add 1 ♦ 6 g of gram (5 · phenyl) in an ice bath to cool the solution. Read the back of the note here.

Page I order base) a B 2 2 - A, 2-trifluoro - 1 liter of THF, (6 ♦ 5 millimoles Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed reverse, and % into the extract 9 Add the ester Ethylene B under the formula B and acid; the acid it} the ο 乙 乙 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4丨水化,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, And layer} 樟{Small water 9 I gram 3 Μ Flash: ο ο Μ Μ 1 1 9 机 ♦ ♦ mixed with retained alkane} ο should be. The paper size applies to the Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 1295281 Α7 ___Β7___ ---------- 1-5, invention description (|〇ϊ) ) 2,2,2-trifluoro- 1 (2-methylphenyl) ) Ethyl ketone oxime 0 — ( 1 0 — camphor oxime sulfonate), which is a colorless liquid ° structure and (please read the back of the note before refilling this page) 1 H — NMR spectrum conformance (CDC13 ) : δ [ppm]: 〇*92(s,3H ),1·12(Ζ)/1·18(Ε)(s,3H) ,1·38 - 1·50(γπ,1Η), 1·55-1·75(γπ,1Η),1·90 - 2·18 (m,3H) , 2·28-2.5 3 (m,5H), 3·25 - 3.38(m,lH) ,3·84(Ζ)/ 3.90(E) (d,lH) , 7.15 - 7,46 (m , 4 Η ) The 〇1 H_NMR spectrum reveals that the product is a mixture of ruthenium and osmium isomers (7:3). The absorption signal is divided into E- and Z-configurations. Example 10: 2,2,2 -trifluoro-l-(2,4-dimethylphenyl)-ethanone oxime- 0 - (1 0 - camphorquinone sulfonate) 10* 1:2,2, 2 — Trifluoro-1(2,4-dimethylphenyl)-Ethyl Ethylene Department Intellectual Property Bureau Staff Consumer Cooperative Printed 30 ♦ 4 g (0 ♦ 286 m) of m-xylene and 34 9 g (0 ♦ 286 mol) of 4-dimethylaminopyridine was mixed in 400 ml of C Η 2 C 1 2 and cooled in an ice bath. 87. 6 g (0 ♦ 657 mol) of A1C12 was added to the solution, and then 60 g (0 · 2 6 6 mol) of trifluoroacetic anhydride was added as a droplet, and the reaction was stirred at room temperature. Mix overnight and pour into ice water, -112- This paper scale applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1295281 Α7 Β7 5. Invention description (, Λ) and KC Η 2 C 1 2 extraction. The organic phase is water-repellent, washed with aq. Na 2 0 0 3 and brine, dried (M g S 0 4 ) and concentrated, and the residue is distilled at 100 ° C / 15 mmHg to obtain 12 6 g of crude product, which is A colorless liquid which can be used directly in the next step without purification. 10,2:2,2,2-trifluoro-l-(2,4-dimethylphenyl)-ethanone oxime 12,6 g (0.062 mol) of 2,2,2-trifluoro-1 One (2,6-dimethylphenyl)-ethanone was dissolved in 30 ml of ethanol (80%), and in this solution, 4 6 g dissolved in 15 ml of water was added in a drip manner. (0 · 066 mol) of hydroxyammonium chloride and 8 ♦ 7 g (0 · 1 〇 6 mol) of sodium acetate, and the reaction mixture was heated under reflux overnight to give a white precipitate. The mixture was poured into ice water and extracted with ethyl acetate. The organic phase K water, NH4 C 1 aqueous solution and brine are washed, dried (M g S 0 4 ) and concentrated to obtain 1 1 ♦ 9 g of crude 2,2,2-trifluoro- 1 one (2,4 one two Methylphenyl)-ethanone oxime, which is a colorless liquid, can be used directly in the next step without purification. 10.3: 2,2,2 —trifluoro-1(2,4-dimethylphenyl)-ethanone oxime- 0 — ( 1 〇—camphor sulfonate) 2 · 0 g (9 · 2 毫The 2,2,2-trifluoro-l-(2,4-dimethylphenyl)-ethane oxime of Moth was dissolved in 20 mL of THF and cooled in an ice bath. Add 2 · 5g to this solution ( -113- This paper size applies to China National Standard (CNS) A4 specification (210x297 mm) (please read the notes on the back ^^ write this page) i line: Ministry of Economics wisdom Property Bureau employee consumption cooperative printed 1295281 A7 B7 V. Invention description (wo) 1 〇, 1 millimol) of 10 - camphor sulfonium chloride, then add 1 · 4 grams as droplets (1 3 • 8 mmol of triethylamine, the reaction mixture was stirred at 0 ° C for 50 minutes, poured into ice water and extracted with ethyl acetate. The organic phase was washed with water and brine, dried (MgSO4) and evaporated. The residue was purified by flash chromatography on silica gel eluting with ethyl acetate and hexane (3:7). 2 g (5·0 mM; 54%) of 2,2,2-trifluoro- 1 (2,4 dimethylphenyl)-ethyl 肟 肟 - (1 〇 樟 樟 樟 醯 醯An acid ester) which is a colorless liquid. The structure is consistent with 1 Η - NMR spectrum ( CDC 1 3 ) : δ C ρ ρ m ] : 0*92(s,3H), 1·12(Ζ)/1·18(Ε) (s'3H), 1 ·3 8 - 1·50 (m,1 Η ) ,1 ·54 - 1 ·80 (m,lH) ,1·90 - 2·58(γπ,11Η), 3*25 - 3·38(ιη, 1Η), 3·83(Ζ)/ 3.88(E) (d,lH) , 7. 〇3 - 7,28 (m ,3 Η ). The 1 H-NMR spectrum revealed that the product was a mixture of hydrazine and hydrazine isomers (3: 2). The absorption signals are divided into Ε- and Ζ-configurations. Example 11: 2,2,2 -trifluoro-1(2,4-dimethylphenyl)-ethanone oxime-0-(1-naphthylsulfonate) 2 ♦ 0 g (9.22 m 2,2,2-trifluoro-i-(2,4-dimethylphenyl)-ethanone oxime (as in Example 10 · 2 -114 - This paper scale applies to China National Standard (CNS) A4 size (210 X 297 mm) (Please read the phonetic transcription on the back? Please write this page urgently) I--------Book ------!·Line Economy Ministry Intellectual Property Bureau staff consumption Co-operative printing 1929281 Α7 Β7 V. Inventive Note (, α) Prepared in 30 ml of THF and cooled in an ice bath. Add 2 ♦ 3 g (1 0 · 1 mmol) of 1 radix sulfonium chloride to the solution, then add 1 · 4 g (13 ♦ 8 mmol) of triethyl arsenide The amine was stirred at 0 ° C for 60 minutes, then poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried (M g S 0 4 ) and concentrated, and the residue K flash chromatography is purified on silica gel. The eluent is ethyl acetate and hexane (3:7). 0 g (7,3 mmol; 80%) of 2,2,2-trifluoro-l-(2,4-dimethylphenyl)-ethanone oxime-0-(1-naphthylsulfonic acid Ester) which is a white solid, γπ·ρ·85 - 124 °C. The structure is consistent with the iH-NMR spectrum (CDCI3): δ [ppm] :1·71 (Ε)/2*03 (Ζ) (s, 3Η), 2·28(Ε)/2*39(Ζ) (s ,3H) ,6·7 7- 7*13(ιη,3Η) ,7·54 — Η 3m /IV 8 7 7 Η IXm /V 3 ο 8 I 5 9 7 (Please read the notes on the back and fill in This page) -1· 1 BiBi |_1 1 I -0' a—· 1 ϋ ϋ atMm l ·ϋ I · 3 2 8 I 5 1Χ 8 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed Η ( 2 things,混 混 混 constitut 7 Ε Ε Ε Ε Χ Χ Χ Χ Χ 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 Ν Ν Ν Ν Ν 1 1 III I 1 4 2, , 2) 2 ί ester, I acid 2 1 sulfonate I 丨 丨 蔡 三 I I I 1 1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 B · 1 1 2 cases} Spring basic paper scale applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. Invention description (w) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed one (2) 5 4 monodimethylphenyl)-ethyl m 肟 (as in Example 1 〇 ♦ 2 prepared) dissolved in 3 〇 ml of T Η F Medium 9 and K ice bath cold SP 0 Add 2 ♦ 3 g (1 0 ♦ 1 mmol) of 2-naphthylsulfonium chloride 9 to this solution. Next, add ♦ 4 g of droplets. 3 Qin 8 millimolar triethylamine $ Stir the reaction mixture at 〇 °c for 6 〇 minutes, then pour it into ice water 9 and Κ ethyl acetate extraction 0 organic phase Κ water and brine wash dry ( Μ g S 0 4 ) and concentrated m $ residue 闪光 Purification by flash chromatography on silica gel f Eluent is ethyl acetate and hexane (3 • 7 ) 9 can get 2 * 1 g ( 5 * 3 mM 5 7 % 2 9 2 $ 2 - trifluoro-1 1 (2 4 - dimethylphenyl)-ethyl hydrazine - 0 - ( 2 - naphthyl sulfonic acid vinegar) $ It is a colorless liquid 0 structure and 1 Η N Μ R Spectrum pay ( CDC 1 3 ) : δ [ PP m ] * 2 • 〇 5 ( Ε ) / 2 • 1 0 ( Ζ ) ( S $ 3 Η ) t 2 * 3 1 ( E ) / 2 ♦ 3 5 ( Ζ ) ( S 9 3 Η ) 6 • 9 2 - 7 ♦ 1 3 ( m 9 3 Η ) 7 • 6 1 - 7 ♦ 7 7 ( m 9 2 Η ) > 7 • 8 8 — 8 ♦ 〇 8 ( m 9 4 Η ) t 8 ♦ 6 1 ( S f 1 Η ) 0 1 Η — N Μ R The spectrum reveals the product as Ζ and E isomer mixture ( 7 : 3 ) 0 Absorption signal is divided into Ε 1 and Z 1 configuration 0 Example 1 3 2 f 2 $ 2 — Fluorine 1 1 (2 > 4 > 6 — Methylphenyl) — B trrjrt ketone oxime — ( 1 〇 樟 樟 藤 ) 1 1 1 1 1 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 116- • ii I 1· i ϋ ϋ ϋ 1§ _1 n 0 ina— I IK—·ϋ ϋ δ, · ϋ βί I n ϋ I ϋ I . (Read the note on the back first? Please fill out this page again. This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. Invention description () 50 · 0 g (0 · 416 mol) of mesitylene And 5 0 · 8 g (0 ♦ 4 1 6 mol) of 4-dimethylaminopyridine was mixed in 6 ml of C Η 2 C 1 2 and chilled in an ice bath. In this solution, 8 7 · 4 g (〇 · 4 1 6 mol) of trifluoroacetic anhydride was added in the solution, followed by Μ - part of the way to add 1 2 8 g (0♦ 957 Mo Ear) of A1C13. The reaction mixture was stirred at room temperature overnight, poured into ice water and extracted with K C Η 2 C 1 2 . The organic phase is washed with water, dried (MgSCU) and concentrated, and the residue is distilled at 1 ΟΟΌ/lmmHg to give 44. 6 g of crude product as a colorless liquid. This crude product can be used directly in the next step without the need of pure ib 0 13. 2:2,2,2 - trifluoro-l-(2,4,6-trimethylphenyl)-ethanone oxime 6.3 g (0·029 mol) of 2,2,2-trifluoro-l-(2,4,6-trimethylphenyl)monoethyl ketone dissolved in 30 ml of ethanol (80 ° C), In this solution, 2.0 g (0. 029 mol) of hydroxyammonium chloride and 4·1 g (0 ♦ 050 mol) of sodium acetate dissolved in 15 ml of water were added as droplets, and refluxed. The reaction mixture was heated overnight, poured into ice water and extracted with EtOAc. The organic phase is washed with brine, dried (M g S 〇 4 ) and concentrated, and the residue is recrystallized from 20 ml of hexane to obtain 1 · 9 g of 2 ' 2 ' 2 - trifluoro-1 (2) , 4, 6-trimethylphenyl)-ethanone oxime, which is white crystal, γπ·ρ·119— 1251° -1 17- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 () Please read the note on the back δ write this page) »!装----订--------- Line Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1295281 A7 B7___ V. Invention Description ((8)) 13*3: 2,2,2-trifluoro-l-(2,4,6-trimethylphenyl)-ethanone ketone oxime~(1〇-樟 樟 醯 sulfonate) Please read the notes on the back and fill out this page. 1. 8g (7.8mmol) of 2,2,2-trifluoro-1(2,4,6-trimethylphenyl)-ethanone The hydrazine was dissolved in 20 mL of THF and cooled in an ice bath. In this solution, add 2 ♦ 2 g (8 · 6 mmol) of 10 - camphor sulfonium chloride, then add 1 ♦ 2 g (11 _ 7 mmol) of three droplets Ethylamine was stirred under stirring for 5 minutes, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried (Mg S〇4) and concentrated. The residue K is purified by flash chromatography on silica gel. The eluent is ethyl acetate and hexane (1:4). Gram (7.6 mol); 97%) 2,2,2-trifluoro-l-(2,4,6-trimethylphenyl)-ethanone oxime- 0 (10 - camphor sulfonate An acid ester) which is a colorless liquid. The structure is consistent with the 1 H - NMR spectrum (CDC 13 ) : δ [ ρ P m ] : 0.92 (s, 3H) , l * 14 (s , 3H ) , l * 40 - l , 49 ( m , lH ) , 1 ·65 -1 · 7 5 (m,1 H ) , 1,93 - 2·47 (m, printed by the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative

1 4 H ) , 3.35 (d, lH), 3.84 (d, lH ), 7*12 (s, 2H). Example 14: 2,2,2 -Trifluoro-1(2,4,6-trimethylphenyl)-ethanone oxime-0-(1-naphthylsulfonate) 2 · 0 g (8 · 7 millimoles of 2,2,2 -trifluoro-l-118- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 Α7 Β7 V. Invention description (〆) one ( 2,4,6-trimethylsulfonyl)-ethanone oxime (Example 13.2 cult.) was dissolved in 40 mL of THF and cooled in an ice bath. In this solution, 2,2 g (9 ♦ 5 mmol) of 1-naphthylsulfonium chloride was added, followed by a droplet of 1 ♦ 3 g (1 3 ♦ 〇 millimolar) Ethylamine was stirred at 0 °C for 150 minutes, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried (MgSCU) and concentrated, and the residue is recrystallized from 5 ml of methanol to obtain 1 ♦ 5 g (3 ♦ 6 mM; 4 1 %) of 2, 2, 2 Trifluoro-l-(1,4,6-trimethylphenyl)-ethanone oxime-(1-naphthyl sulfonate) as a white solid, mp 1 37 - 145 °C. The structure is consistent with 1 Η-NMR spectrum (CDC 1 3 ) · δ [ppm] : 1,88 - 2,39 (m , 9Η) , 6·49-7·12 (ιη, 2Η) , 7·56 a 7.72 (m, 3H), 8,00 (t, lH),

8*22 ( d * 1 H ) »8*37 — 8- 54 (m,2H )° Example 15 : 2,2,2 —trifluoro-1—(2,4*,6 —trimethylphenyl ) 一乙画肟0—(2-Naphthylsulfonate) 2 ♦ 0g (8 · 7mmol) 2,2,2~Trifluoro Igong one (2,4,6 —Third The phenyl) acetamidine 8 (prepared in Example 13 · 2) was dissolved in 50 mL of THF and cooled in an ice bath. In this fatigue, 2 2 g (9 ♦ 5 mmol) of 2-naphthyl chlorofluorene-119- is applied to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) - ------------装--- Please read the notes on the back HI to write this page) Order · --Line - Ministry of Economic Affairs Intellectual Property Bureau employees consumption cooperatives printed 1295281 Α7 Β7 5, invention Illustrate (w) the compound, then add 1 ♦ 4 g (1 4 ♦ 3 mmol) of triethylamine in the form of droplets, stir the reaction mixture for 2 10 minutes at Ot:, pour into ice water, and Κ Extracted with ethyl acetate. The organic phase is washed with water and brine, dried (Μ g S 0 4 ) and concentrated, and the residue is recrystallized from hexane and ethyl acetate (9:1) to give 1 ♦ 5 g (3 ♦ 6 mmol) 41%) of 2,2,2-trifluoro-1(2,4,6-trimethylphenyl)-ethanone oxime-0-(2-naphthyl sulfonate), which is white

Solid, m. p · 106 - 1 131. The structure is consistent with 1 H - NMR spectrum (C D C 1 3 ) : δ [ p p m] : 2 · 2 1 ( s

,3H) ,2*30(s,6H) ,7·01 (s,2H ),7·63 - 7,7 6 (m,2H) ,7,96(t,7 2 Η ) ,8*03 (d, 2H) , 8, 62 (s, 1H) ο Example 1 6 : 2,2,2 —trifluoro-l-(4-methoxyphenyl)-e-ketoneoxime-methylsulfonic acid Ester 1 6 ♦ 1 : 2,2,2 —trifluoro-l-(4-methoxy-methoxy)-e-ketone 29 ♦ 0 g (0 · 268 寞) of anisole and 32 ♦ 8 g ( 0 ♦ 268 moles of 4-dimethylaminopyridine was mixed in 3 mL of C Η 2 C 1 2 and cooled in an ice bath. Add 56 · 3 g (0 ♦ 26 8 m) of tri-glycolic anhydride to the solution of @ Κ Κ droplets, followed by Μ - part of the way to add 8 2 ♦ 2 $ ( -120- The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) --------------Installation --- (Please read the note on the back first H write this page) : Line - Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1295281 Α7 Β7 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed V. Invention Description (A) 〇· 6 1 6 Mo) A 1 C 1 3 . The ruminant mixture was stirred at room temperature overnight, poured into ice water, and extracted with M C Η 2 C 1 2 . The organic phase is washed with water, dried (M g S 0 4 ) and concentrated, and the residue is purified by flash chromatography on silica gel eluting with ethyl acetate and hexane (5: 9 5 ) to obtain 3 7 · 8 g The crude product is a brown liquid. 16,2:2,2,2-trifluoro-l-(4-methoxyphenyl)-B-infrared 3 7·2 g (0·182 mol) of 2,2,2-trifluoro 1 1-(4-methoxyphenyl)-ethanone was dissolved in 150 ml of ethanol (80), and in this solution, 13 ♦ 3 g dissolved in 75 ml of water was added as a droplet. (0 · 191 mol) hydroxyammonium chloride and 2 5 ♦ 4 g (0 ♦ 3 0 9 mol) of sodium acetate, the reaction mixture was heated under reflux for 4 hours, poured into ice water, and the precipitate was filtered to obtain 30 ♦ 0 g of 2,2,2-trifluoro-l-(4-methoxyphenyl)-ethanone oxime, which is a pale yellow solid. The crude product can be used directly in the next step without purification. : 2,2,2-trifluoro-l-(4-methoxyphenyl)-ethanone ketone-o-(methylsulfonate) 6 · 5 g (30 ♦ 0 mmol) of 2, 2,2-Trifluoro-l-(4-methoxyphenyl)-ethanone oxime is dissolved in 25 ml of THF and cooled in an ice bath. In this solution, 3 ♦ 8 g (3 3 ) ♦ 0 millimoles of methane sulfonium chloride, followed by droplets People 4.6 g (45 · 0 mmol) of triethylamine was stirred at square t -121- (Read back surface

I n I Note H Pack--- Write this page) · • Line: This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. Invention Description (w) (Please Read the notes on the back first. 3 Write this page. The reaction mixture was poured into ice water for 5 hours, and extracted with ethyl acetate. The organic phase is washed with water and brine, dried (M g S 0 4 ) and concentrated, and the residue is recrystallized from 15 ml of ethanol to give 5 ♦ 9 g (20·0 mmol; 67%) of 2 , 2, 2 -Trifluoro-l-(4-methoxyphenyl)-ethanone oxime-(methylsulfonate), which is a white solid, m, p. 47 - 5 leC. The structure is consistent with 1 Η - NMR spectrum (CDC13) : δ [ppm] : 3 * 2 7 ( s

,3H) ,3*88(s,3H) ,7 00(d,2H ),7*55(d,2H) 〇Example 17 : 2,2,2 —trifluoro- 1 -1 (4-methylsulfuric) Phenyl phenyl) acetoin-methyl methacrylate 17,1:2,2,2-trifluoro-l-(4-methylthiophenyl)-ethyl hydrazine 5 0 · 0 g (0 ♦ 4 0 3 Mo) Thioanisole and Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 49 · 2 g (0 ♦ 403 mol) of 4-dimethylaminopyridine in 500 ml Mix in C Η 2 C 1 2 and cool in an ice bath. In this way, 84. 6 g (0 · 403 mol) of trifluoroacetic anhydride was added to the solution of the helium droplets, and then 1 2 3 g (0 · 9 2 6 Mo) was added in one part. Ear) A 1 C 1 3 . The reaction mixture was stirred at room temperature overnight, poured into ice water, and extracted with EtOAc EtOAc. The organic phase is washed with water, dried (M g S 0 4 ) and concentrated to give 5,0 g of 2,2,2-trifluoro-l-(4-methylthiophenyl)-B-122. - This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 Α7 Β7 5. Inventive Note (Anthrone, which is a yellow solid. The crude material can be used directly in the next step without purification. -------------装--- (Please read the note on the back first to write this page) 1 7 ♦ 2 : 2,2 , 2~trifluoro-i-(4-methyl Thiophenyl)-ethanone oxime 49 ♦ 3 g (0,224 mol) of 2, 2, 2 trifluoro- 1-(4-methylthiocarbyl)-monoethyl ketone dissolved in 250 ml of ethanol Medium (80 ° C) 'In this solution, K droplets were added to 16 · 3 g (0 ♦ 235 mol) of hydroxyammonium chloride and 31 ♦ 2 g (〇. 381) dissolved in 125 ml of water. Sodium acetate of methanol, refluxing the reaction mixture for 6 ♦ 5 hours, pouring into ice water, filtering out the precipitate to obtain 51 ♦ 1 gram of 2,2,2 trifluoro- 1 (4-methyl sulphide) Phenyl) acetonitrile 8 bow 'its yellow solid The crude product can be used directly in the next step without purification. Line 17 , 3 : 2,2,2~trifluoro-indolyl (4-methylthiophenyl)-ethyl hydrazine- 0- (A Base sulfonate) 5 . 9 g (25 · 〇 mmol) of 2, 2, 2 Trifluoro-Important Intellectual Property Office Staff Consumer Cooperative Printed 1 (4 Methylthiophenyl) The ethyl ketone oxime was dissolved in 30 ml of THF and cooled in a K ice bath. In this solution, 3 ♦ 2 g (2 8 ♦ 0 mmol) of methylsulfonium chloride was added, followed by hydrazine droplets. 3·8 g (38,0 mmol) of triethylamine was added, and the reaction mixture was stirred at 〇 °c for 5 hours, poured into ice water and extracted with ethyl acetate. The organic phase was washed with water and brine. Dry (MgS〇4) and concentrate, the residue is recrystallized from 30 ml of ethanol to obtain 3 · 9 g ( -123- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 public) 1295281 _ Β7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (〆) i 2 ♦ 4 millimoles; 5 〇%) 2,2,2-trifluoro-1 (4-methylthiophenyl)~ethanone oxime (methanesulfonic acid _), which is a pale yellow solid, m ♦ p · 8 7 - 90 ° C. Structure and 1 Η - NMR spectrum Match (CDC 1 3 ) : δ [ ppm ]: 2 '52 (s,3H) ,3,26 (s,3H), 7*31 ( d,2 Η ) ,7 ♦ 4 7 ( d,2 Η ) Spring Example 18: 2,2,2 -trifluoro-1(3,4-dimethoxyphenyl)-ethyl-hydrazine-methylsulfonate 18· 1 :2' 2' 2 — Trifluoro-1(3,4-dimethoxyphenyl)-ethoxime 13,8 g (0♦ 10 mol) of 1,2-dimethoxybenzene and 12,2 g (0 ·10) The 4 dimethylaminopyridinium of Mohr was mixed in 75 ml of C Η ζ C 1 2 and cooled in an ice bath. In this solution, 2,0 g (0 * 10 mol) of trifluoroacetic anhydride was added in the form of ruthenium droplets, and then 3 2 · gram (〇♦ 2 4 mol) was added in part. ) A 1 C 1 3 . The reaction mixture was stirred at room temperature overnight, poured into ice water and extracted with EtOAc. The organic cypress K is washed with water, dried (M s S 0 4 ) and concentrated, and the residue is purified by flash chromatography on silica gel. The eluent is ethyl acetate and hexane (1: 9 ), and 2 9 g can be obtained. White solid product. 18.2: 2,2,2 —trifluoro-l-(3,4-dimethoxyphenyl)-ethoxime-124- (please read the back I ϋ 1— ϋ n 1· I Installation - Write this page) Line: This paper scale applies China National Standard (CNS) A4 specification (210 X 297 mm) !295281 A7 B7 Five Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing, invention description (N) - -------------装--- (Please read the note on the back first, HI write this page) 2,9 grams (9·7 millimoles) of 2,2,2—three Fluorine-1~(3,4-dimethoxyphenyl)-ethoxime is dissolved in 12 ml of ethanol (80 ° C), and in this solution, the droplets are added and dissolved. 0 ♦ 8 3 g (1 2 ♦ 0 mmol) of hydroxyammonium chloride in 6 ml of water and 1 ♦ 2 g (1 5 ♦ 0 mmol) of sodium acetate. The reaction mixture was heated under reflux for 7 ♦ 5 hours. Into ice water, extract with hydrazine ether, wash the organic phase with water and brine, dry (M g S 0 4 ) and concentrate to obtain 2 ♦ 3 g of 2,2,2-trifluoro-1 (3,4 Dimethoxyphenyl)-ethanone oxime, the crude product can be directly used in the next step Used without purification. 18*3:2,2'2-trifluoro-l-(3,4-dimethoxyphenyl)-e-ketoneoxime-methylsulfonate-line- 2 ♦ 3 g (9 ♦ 0 The millimolar 2,2,2-trifluoro-l-(3,4-dimethoxyphenyl)-ethanone oxime was dissolved in 20 mL of THF and cooled in an ice bath. To this solution, add 1.2 g (10 ♦ 〇 mmol) of methylsulfonium chloride, then add 1 ♦ 5 g (15 ♦ 〇 mmol) of triethylamine as a droplet. Hey. The reaction mixture was stirred under stirring for 5 hours, poured into ice water and extracted with ethyl acetate. The organic cypress water and brine are washed, dried (M g S 0 4 ) and concentrated, and the residue is recrystallized from 15 ml of ethanol to obtain 2 ♦ 2 g (6 ♦ 7 mmol; 74%) of 2 , 2,2 -trifluoro-l-(3,4-dimethoxyphenyl)-ethanone oxime-(methylsulfonate), which is a white solid, m·p · 10 5 -107 °0. The structure is consistent with 1 Η — NMR spectrum (CDC 1 3 ) : δ [ppm]: -125- This paper scale applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. Description of invention (tA 3*27 (s,3H) ,3·91 (s,3H), 3,9 5 ( s , 3 Η ) , 6 ♦ 9 6 ( d , 1 Η ), 7*05 ( s , 1 Η ) , 7 · 2 〇(d , 1 Η ) ° Example 1 9 : 2,2,3,3,4,4,4 hexafluoro- 1 phenyl-butanthene-0- (1 〇 樟 樟 樟 醯 acid Ester) 19·1:2,2,3,3,4,4,4-heptafluoro-l-phenyl-butanone 肟10 g (0 ♦ 037 m) 2,2,3,3 4, 4, 4 a t: Fluorine- 1 Benzene g-butan is dissolved in 30 ml of ethanol (80 ° C), in this solution, Μ 'droplet method has been dissolved in 15 ml 2 · 6 g (0 ♦ 038 mol) of hydroxyammonium chloride in water and 5 ♦ 1 g (0 ♦ 〇6 2 mol) of sodium acetate. The reaction mixture was heated under reflux for 6 hours and poured into ice water to give acetic acid Ester extraction, organic phase washed with brine, dried (MgS〇4) and concentrated. Residue recrystallized from 5 ml of hexane 4·7 g of 2,2,3,3,4,4,4-t-fluoro-1-phenyl-butanone-Jiang' is a white solid, m ♦ ί> · 57 - 60oC〇19,2 :2,2,3,3'4'4'4-heptafluoro-l-phenyl-butanone oxime- 0 — ( 1 〇 樟 樟 樟 2 2 2 2 2 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 2,2,3,3,4,4,4 hexafluoro- 1 -phenyl-butanone oxime in 4 liters of THF, and cooled in an ice bath. Add 2 · 9g ( -12 6- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the note on the back 3 to write this page) Order: Line: Ministry of Economic Affairs Intellectual Property Office staff Consumer Cooperatives Printed 1295281 A7 B7 V. Invention Description (1 1 ♦ 6 millimoles) of 1 〇 - camphor sulfonium chloride, followed by droplets of 1 · 6 grams (1 6 · 0 millimoles The triethylamine of the ear was stirred at 〇 ° C for 4 ♦ 5 hours, poured into ice water' and extracted with ethyl acetate. The organic phase is washed with water and brine, dried (M g S 0 4 ) and concentrated, and the residue is purified by chromatography on silica gel eluting with ethyl acetate and hexane (1: 9 ) to obtain 2 ♦ 3 g ( 4 ♦ 6 mM; 4 3 〇/〇) 2,2, 3, 3, 4, 4,4—ir fluoro-1 phenyl-butyrene-0—( 1 〇- camphor sulfonate Ester), which is a pale yellow liquid, the structure is consistent with 1 Η NMR spectrum (CDC 1 3 ): 5 [ppm]: 0*92 (s, 3H), 1·12 (Ζ) / 1.18 (E) (s ,3H) ,1·40 - 1·50(γπ ,:ίΗ) ,1·66 - 1·73(ιη,1Η) ^1-92 A 2*18(m,3H) ,2·31 - 2* 54(m, 2Η), 3·28(Ζ)/3·33(Ε) (d,lH),3·83(Ζ)/3·93(Ε) (d,lH), 7.37 - 7·63 (m, 5H) Printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs (please read the following notes on the back page) 1 H — NMR spectrum reveals that the product is a mixture of Z and E isomers (3: 2). The absorption signal is divided into E- and Z-configurations. Examples 2 0 - 3 6 : The compounds of Examples 2 0 to 3 6 can be prepared according to the method described in Example 1-2 using a relative educt. Table 1 : -127- This paper scale applies to China National Standard (CNS) A4 specification (210 < 297 mm) 1295281 A7 B7 V. Invention description (w) ra\ II D ^c=n-o-s-rb 〇 f3c

Example 2 结 knot R A structure

R B

Ch3〇{^ Purification method Status: m p ( °C ) (Please read the note on the back to write this page) Recrystallized from white solid in ethanol 112-115 Printed by the Intellectual Property Office of the Ministry of Economic Affairs

1 H-NMR [0' (ppm) ] : 2 . 48 ( s , 3H) , 3. 87 (s , 3H), 6.97 (d, 2H), 7.38 (d, 2H), 7.46 (d, 2H) , 7.90(d,2H) Example 2 1 Structure Purification Method Status: mp ( °CRARB ch30 -CK -〇-〇ch3 Recrystallized from white solid in methanol 94-97 -128 This paper scale applies to China National Standard (CNS) A4 Specifications (210 X 297 mm) Line. 1295281 A7 B7 V. Description of invention (, 〆)

1 Η, Ν Μ ϋ [ δ ( PP ffl ) ] : 3 · 8 5 ( s, 3 Η ), 3 · 9 0 ( s , 3 Η ), 6.97 (d, 2H), 7.03 (d, 2H), 7.46(d,2H), 7.95(d,2H) purification method state: mp ( °C ) RB

Example 2 2 Conclusion R A - -----------% (Please read the note on the back of the 3rd and then fill out this page) Printed by the Intellectual Property Office of the Ministry of Economic Affairs

Chromatography (hexane yellowish liquid: ethyl acetate = 95:5) 1H-NMR [5 (ppm)]: 0. 7 3 - 1 . 7 9 (in, 23H) , 2 . 4 8 - 2 . 8 5 (id, 2H), 3.85 (s, 3H), 6.97 (d, 2H), 7.30-7.39 (ffi, 2H), 7.45 (d, 2H), 7 · 8 8 - 7 · 9 5 ( ra, 2 Η) Example 2 3 Structure purification method Status: mp ( °C ) RARB ch3〇_Q_ _Q_ c12h2: Order --------- Line _ ch3ohQh- -C8Hi7 -129- This paper scale applies to Chinese national standards (CNS) A4 size (210 X 297 mm) 1295281 A7 B7 V. Description of invention (〆) (Please read the notes on the back 3 to write this page): Ethyl acetate = 9:1) 1 H-NMR[S (ppm) ] : 0 . 87 (t , 3H) , 1. 21-1 . 52 (in, 10H) , 1.82- 1.92 (ro, 2H), 3.39 (t, 2H), 3.37 (s, 3H), 6.99(d,2H), 7.54(d,2H) Example 2 4 Structure Purification Method Status: mp ( °C ) RAR Β ~0^〇ch3 Recrystallized from the hexane/white solid ethyl acetate 85-86 1 H-NMR[a (ppm)] printed by the Bureau of Staff and Consumers of the Property Bureau: 2.51 (s, 3H), 3.91 (s, 3H), 7.04 (d, 2H), 7 · 2 8 (d, 2 H ), 7 · 3 7 ( d, 2 H ), 7 · 9 5 ( d, 2 H ) Example 2 5 Structure purification method Status: mp ( °C )

R A R B -130- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm)

Example 2 6 knot RA 1295281 A7 _B7 V. Inventive Note (y)) Chromatography (hexane yellow liquid: ethyl acetate = 95:5) 1 H~NMR [5 (ppm) ] : 0.75-1 . 78 (m , 23H) , 2 . 52 (E) (s , 3H), 2.54-2.85 (ι, 2Η), 7.02-7.43 (ffl, 6H), 7.8 8- 7.95 (m, 2H) Structure purification method Status: mp ( t )

R B (please read the precautions on the back 3 write this page) · ·

CH3S ο- • c8h17 Chromatography (hexane white solid: ethyl acetate 40-41 = 95:5) • Line” Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed 1 H-NMR [5 (ppm)]: 0.82 ( t,3H),1.13-1.31(ini8H),1.33-1.43(m,2H),1.74-1.84(ffl,2H),2.45(s,3H),3.33(t,2H), 7 · 2 4 (d , 2 Η) , 7 · 3 8 ( d , 2 Η ) Example 2 7 -131- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. Invention description (4) Structure purification method status: m ρ ( υ )

RARB is recrystallized from white solid in toluene 122-128 1 H-NMR [S (ppm)]: 2.52 (s, 3H), 7. 28 (d, 2H), 7.37 (d, 2H) 7.65-7.77 (in, 2H), 7.92-8.07 (ni, 4H), 8.62 (s, lH) (Please read the notes on the back _ write this page)

Example 2 8 knot R A structure

RB Purification method status: mp ( °C ) • Line “-CH3 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed Chromatography (hexane white solid: ethyl acetate 58-60 = 4:1) 1 H-NMR[5 (ppm)]: 2.19(E)/2.38(Z)(s,3H), 3.25(s,3H), 7 · 1 7 - 7 · 4 7 (in,4 Η ).Z : E = 1 : 1 -132- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 Α7 Β7 V. Invention description (d) Example 2 9 Structure purification method Status: mp ( °C )

R A

RB h3c- -C6Hs Recrystallized from white solid in ethanol 63-75 1 H-iNMR [5 (ppni)]: 2.40 (s, 3H), 7.20-7.35 (in, 4H), 7.53-7 · 7 6 (in , 3 Η ), 8 · Ο 3 ( d , 2 Η ).

Example 3 Ο junction R A structure

RB (please read the precautions on the back\^ write this page) Purification method status: mp ( °C ) Pack-----I--book---------line ci- -C6H5 Economy Ministry of Intellectual Property, Staff Consumer Cooperative, Printed Chromatography (hexane white solid: ethyl acetate 6 8 - 7 6 = 9:1) 1 H-NiMR[5 (ppifl) ] :7 . 3 3 - 7 . 7 8 (ια,7Η) ,7.9 7 - 8.0 8 (ιπ,2Η) -133- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. Description of invention (

Example 3 Junction R A structure Purification method 'state: m p ( °C )

R α - and / 3-naphthalene-C Η 3 - based mixture chromatography (hexane brown solid yellow ethyl acetate 55-57 5:1) 1 H-iNTMR [5 (ppm) ] : 3 . 2 5 / 3 . 2 7 / 3 . 3 0 (s,3H) , 7. 4 7 - 8.0 5 (1, 7H), ct-,/5-, E-, Z-isomer mixture

Example 3 2 knot R A structure

R Purification method status: mp ( °C ) -------------------- Order --------- line (please read the notes on the back first) Fill in this page) Printed by the Intellectual Property Office of the Ministry of Economic Affairs

-CH3 crystallization (hexane yellow oil: ethyl acetate = 5:1) 1H-NMR [S (ppm)]: 3.24 (s, 3H), 4.04 (s, 2H), 7. 19. , 9Η), 134- This paper size applies to China National Standard (CNS) A4 specification (210 x 297 mm) 1295281 Α7 Β7 V. Invention Description (Al) Example 3 3

R A

Or 〇-(CH2)2-i

Structure

R Purification method state ·· mp ( °C ) CHs chromatography (white solid CH 2 Cl 2 92-96 = 4 : 1) 1 H-NMR [5 (ppm)]: 3.24 (s, 3H), 4.31-4.40 (ffl , 4H), 6.92-7·07 (πι, 5Η), 7.28-7.33 (ffl, 2H), 7.51-7.61 (io, 2H)

Example 3 4 Structure RAR Purification Method Status: mp ( °C ) --------I----Install--- (Please read the back note before writing this page) • Line: a - and / 9 'Naphthalene-C3 H7 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed mixture chromatography (hexane yellow oil: ethyl acetate = 5:1) 1 H-NiMR [5 (ppm) ] : 1. 11 (t , 3H) , 1. 99 (πι, 2H) , 3 . 39 (t , 2H), 7.44-8.02 (ffl, 7H); a-, /3-, Ε-, Ζ-isomer mixture- 1 3 5 - This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. Invention description (, p)

Spring example 3 5 knot R A structure Purification method State: m p ( t:)

R

C3 H7 chromatography (hexane yellow oil: ethyl acetate = 5:1) (Please read the note on the back to write this page) 1 Η- ΝΜΜδ (ppffl)]: 1.08(t,3H), 1.90U ,2H),3.39(t,2H), 7 · 1 9 - 7 · 4 3 (πι,9 Η )

Example 3 6 knot R A

Purification method Status: m ρ ( Ό ) R B -- Line - Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative

Cs H7 precipitation (white solid, 130 C2 H5 OH/

Hz 〇) -136- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 Example 3 7 :

Formula I I I compound, R i is

-------------- (Please read the note on the back first H write this page) Order _ · Ministry of Economic Affairs Intellectual Property Bureau employees consumer cooperatives print examples 3 7 compounds can be 2 Mo The relative enthalpy and 1 mole of the relative chloride were prepared according to the procedure of Rex. 2-1. This compound was obtained as a white solid, m.p. 1 Η — NMR data [ppm] : 7*〇0 — 7—13 (m,8H) , 7·2〇-7*28 (m,2H) , 7,38 - 7.48 (m, 8 Η ) , 7*87(t,lH) , 8.36(d,2H) ,8,63(s,lH) 〇Example 3 8 : CH^OS_0一N \\ V'c 〇-(CH2)2- NO— S〇2CH3 cf3 137- Wood paper scale applies to China National Standard (CNS) A4 specification (210 x 297 mm). Line 1295281 A7 B7 V. Description of invention ((10)) Compound of formula II, R i is Ο 〇-(ch2) 2- 〇R2 is F ; R3 is a S〇z CH3

The compound of Example 38 can be prepared from 1 mole of the relative biguanide and 2 moles of the cytidine chloride according to the procedure of 洌1 ♦ 2, which is isolated by chromatography (hexane: ethyl acetate) 5:1), as a pale yellow liquid, iH-NMR data [ppm]: 3.25/3.27 (s, 6H), 4*43 (s, 4H), 7, 〇2 - 7·08 (m, 4H), 7*53 — 7.62 (m, 4H Example 3 9 (Please read the note on the back first to write this page) Printed by the Consumer Intellectual Property Office of the Ministry of Economic Affairs

C3H702S Ο一Ν /C P3C Ο

〇-(CH2)2-C N-O-S〇2C3H7 SCF,

The compound of formula I I* R is 〇-(CH2)2- o -138- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 Printed by the Intellectual Property Office of the Ministry of Economic Affairs

V. INSTRUCTION DESCRIPTION (π) Rz is F; R3 is a S〇zC3H7'. The compound of Example 39 can be prepared according to the method of Example 38. This compound was isolated by chromatography (hexane: ethyl acetate (5:1), as an orange liquid, 1 Η - NMR data [ppm]: 1 · 12 (t , 6 Η ) , : L, 88 - 2 *02(m,4H) ,3,34- 3·43(ιη,4Η) ,4.43(s,4H) ,7*〇一7·〇7 (m,4H) ,7·51 - 7·61 ( m, 4 Η ). Example 4 Ο - 7 4 : The compounds of Examples 4 to 7 4 were prepared according to the method of Example 1-2, using berberine to isolate, and their structures and data are listed in Table 2. Table 2 : ra\ II 乂一 SR〇F3C Example 4〇Structure RAR 〇Purification method Status: mp ( °C ) -139- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) Please read the back first Precautions

1295281 A7 B7 V. Description of invention (from) ch3s h3c

H, NMR [S (ppin)]: 2.34 (s, 3H), 2.52 (s, 3H), 2.60 (s, 6H) • 04 ( s, 2H) , 7.29 (d, 2H), 7.38 (d, 2H) Spring Example 4 1 purification method state: mp ( ° C )

R A

R B ch3〇 <y~

Ch3 h3c Recrystallized from white solid in methanol 101-102 Printed by the Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative 1 H-NiMR[5 (ppro)]: 2.34(s,3H), 2.60(s,6H),3.87(s ,3H), 6 · 9 6 - 7 · 0 3 (in,4 Η ),7 · 4 6 ( d , 2 Η ) Example 4 2 purification method state: mp ( °C ) 140- (please read the back first) Note on this page)

This paper scale applies to China National Standard (CNS) A4 specification (210 297 297 mm) 1295281 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing A7 B7 V. Invention description u?)

R A R B 〇~. Servo-ch3 chromatography (hexane white solid: ethyl acetate 71 - 73 = 4:1) 1 Η - NMR [ δ (PPift)] : 3 · 26 (s , 3H) , 7 · 06 (d , 2H) , ll(d, 2H) 7·24(t, 1Η) , 7 · 43 (t , 2H), 7 • 53(d, 2Η) Example 4 3 Structure Purification Method Status: mp (tn RARB h3c) / CH3 〇j chromatography (hexane: ethyl acetate pale yellow liquid = 85:15) 1 H-NMR [5 (ppm)]: 0.93 (t, 3H), 1 · 13 (s, 3H), 1.40 -1 . 48 (in,1Η),1·67-1·75(ιιι,1Η),1·93-2·18(ια,3Η),2.33-2.46( m,2H),2.52(s,3H ), 3.34(d,lH),3.85(d,lH),7.32(d,2H), 7.47 (d, 2H) -14 1- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 PCT) (Please read the phonetic on the back first? Please fill out this page again)

1295281 A7 B7 V. Description of invention (

Example 4 4 knot R A structure purification method state: m p ( t )

R ch3o-^>- Recrystallization from white solid in methanol 85-87 1 H-NMR [5 (ρρι)]: 3.87 (s, 3H), 6.98 (d, 2H), 7.46 (d, 2H), 7.6 3-7.76 (ιπ, 2Η), 7.93-8·00 (δΐ, 2Η), 8.03 (ά, 2Η), 8.63( s, 1Η)

Example 4 5 knot R A structure

RB (Please read the note on the back and fill out this page) —————————— II ·11111111 · Purification method status: mp (Ό) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed h3c., CHn ch3o v〇 layer Analysis (hexane colorless liquid: ethyl acetate = 3:1) -142 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 public) 1295281 A7 B7

V. INSTRUCTIONS (M) 1 H > NMR [ δ ( PP m ) ] : 0 . 9 3 ( s , 3 H ) , 1. 1 4 ( s , 3 H ) , 1. 4 0 - 1 . 4 9 (in, 1H), 1.68-1.77 (ffl, lH), 1.93-2.18 (m, 3H), 2.35-2.46 (m, 2H), 3.35 (d, lH), 3.85 (d, lH), 3.88 ( s,3H), 7.00(d,2H), 7. 5 4 ( d , 2 H ) Example 4 6 Structure purification method Status: mp ( °C ) RARB ch30-^^—

One C

P Recrystallized from hexane/white solid ethyl acetate 81-82 1H-NMR [5 (ppm)]: 3.84 (s, 3H), 4.68 (s, 2H), 6.93 (d, 2H) 7.36 (d, 2H), 7.42 (s, 5H) --------- Order ---------· (Please read the notes on the back and fill out this page)

Ministry of Economic Affairs, Intellectual Property Bureau, employee consumption cooperative, printing

Example 4 7 Structure R A R Purification Method Status: m p ( °C )

Recrystallization from white solid in hexane 87-88 -143- This paper scale applies to Chinese National Standard (CNS) A4 specification (210 x 297 mm) 1295281 A7 B7 V. Description of invention (_) 1 H-NMR [S (ppm ) ] : 1 . 21 (d, 12H) , 1. 28 (d, 6H) , 2. 93 (in, 1H) 3.88 (s, 3H), 4.06U, 2H), 6.98 (d, 2H), 7.19 (s, 2H), 7.49 (d, 2H)

Spring Example 4 8 knot R A structure Purification method State: m p ( °C )

R B

Qr°JOr

CH, h3c Recrystallized from white solid in hexane 78-80 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed 1 H-NMR [5 (ppm) ] : 2.35 (s, 3H) , 2.60 (s, 6H), 6.9 8 - 7.0 7 (1, 4 H ),7 · 1 0 ( d,2 H ),7 · 2 3 (t,1 H ),7 · 3 9 - 7 · 4 7 (in,4 H ) Example 4 9

R A structure

R B Purification Method Status: m p ( °C ) -1 4 4 (Please read the notes on the back and fill out this page)

This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mil) 1295281 A7 B7 V. Description of invention (μΗ) CH, CH3O-Q)— CH, Chromatography (hexane light yellow liquid: ethyl acetate = 5:1) 1 H-SMR[<5 (ppffl)]: 1.47(d,6H),3.81(ni,lH),3.87(s,3H) 7 · Ο Ο ( d,2 Η ),7 · 5 3 ( d, 2 Η )

Example 5 〇 junction R A structure purification method state: m p ( °C )

RB-C3H7 Chromatography (hexane white solid: ethyl acetate 69-70 = 5:1) Printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs 1 Η - ιΝ7 MR [ δ ( Ρ Ρ i) ] : 1 . 1 2 (t , 3 Η ) , 1. 9 4 (in, 2 Η ) , 2 . 5 3 ( s , 3 Η ), 3 · 3 9 (t, 2 Η ), 7 · 3 0 ( d, 2 Η) ,7 · 4 5 ( d,2 Η ) Example 5

R A structure

R Purification method Status: m ρ ( °C ) -145- (Please read the notes on the back and fill out this page)

This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 ____B7 V. Description of invention (

(Please read the note on the back and then fill out this page) Recrystallization from hexane/white solid ethyl acetate 51-52 1 H-NMR [<5 (ppm)]: 1.47 (d, 6H), 2.52 (s53H) ), 3.80 (ia, lH), 7.32 (d, 2H), 7.46 {d, 2H) Example 5 2 Structure Purification Method Status: mp ( ° C )

RARB ch3s^Q)_ -C4 Hg Chromatography (hexane colorless liquid: ethyl acetate = 5:1) Printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs 1 H-iNMR [5 (ppm) ] : Ο . 96 ( t , 3H) , 1. 49 (in, 2H) , 1. 87 (m, 2H), 2.53 (s, 3H), 3.40 (t, 2H), 7.32 (d, 2H), 7.46 (d, 2H) Example 5 3 Structure Purification Method Status: mp ( t ) - 146- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. Description of invention (

R A

</ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; , 2H) 3.42 (t, 2H), 3.87 (s, 3H), 7.00 (d, 2H), 7.54 (d, 2H)

Example 5 4 Structure R A R B Purification method Status: m p ( °C )

Qr^r Chromatography (hexane white solid: ethyl acetate 90-91 = 5:1) 1 H-NMR[(5 (ppffl)]: 3.93 (s, 3H) printed by the Intellectual Property Office of the Ministry of Economic Affairs , 6.98-7.12 (ia, 6H), 7.22 (t, lH), 7.38-7.46U, 4H), 7.95 (d, 2H) Spring Example 5 5 147- (Please read the note on the back and fill out this page)

This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. Description of invention (Μ) Structure Purification method Status: m P ( °C )

R

R 〇-°~〇- OCl^ * 2-3⁄4 II Θ色@1 fl Recrystallization 147-148 1 H-NMR[5 (ΡΡΐ) ] :7.03 (d,2H) , 7. 09 (d , 2H ), 7 . 2 1 (t , 1H), 7.38-7.45 (in, 4H), 7.63-7.77 (in, 2H), 7.92-8.04 (iii, 4H), 8.63 (s, 1H)

Example 5 6 knot R A structure

RB Purification method status: mp ( °C ) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing chromatography (hexane brown liquid: ethyl acetate = 9:1) 1 (ρριη)]: 0.93 (ιη, 3Η), 1 . 2 0 - 1 . 4 0 (πι,8Η), 1.40- 1.54(m,2H),1.88(Z)/2.05{E)(ffl,2H), 3.42(Z)/3.65(E)( -148 - (Please read the notes on the back and fill out this page)

This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 Α7 Β7 V. Invention description (μ) t , 2 Η ) , 7 . 0 0 - 7 . 1 2 (in, 4 Η ) , 7 . 2 2 (t , 1 Η ) , 7 . 4 0 (t , 2 Η ) , 7 . 5 0 ( (1,2[〇, £:2 = 1:3 absorption peak signal shows £- and &quot Isomer

Example 5 7 Structure RAR Purification method Status: mp ( °C ) /CH3 H3C-°r CH3 For example / pu H3C-fH 3 CH, chromatography (hexane white solid: ethyl acetate 70-72 = 6:1) 1 H-NMR [S (ppm) ] : 1 . 17-1 . 30 (πι, 18H) , 2 . 93 (si, 1H) , 4 . 05 ( πι, 2Η), 6·98-7·12 (ίπ , 4Η),7·15-7·27(ι,3Η),7·37-7·48(πι, 4H) Example 5 8 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed Purification Method Status: mp ( ° C )

R A

R o·. Ch3 - CH \ ch3 Chromatography (B alkane white body: ethyl acetate 67-68 = 5:1) -149- (Please read the back note and fill out this page)

This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. Description of invention ( 1 H-NMR [(5 (ρρπι) ] : 1 . 48 (d , 6H) , 3 . 82 (ία, 1H) , 6. 98-7 . 12 m, 4H), 7.22 (t, lH), 7.43 (t, 2H), 7.50 (d, 2H)

Example 5 9 knot R A structure

R Purification method status: mp ( °C ) (Please read the note on the back and fill out this page) -c4 Hg chromatography (hexane colorless liquid: ethyl acetate = 8:1) 1 H-NMR [5 (ppm ) ] : : Ο . 98 (t , 3H) , 1. 50 (id , 2H) , 1. 88 (in, 2H), 3.41 (t, 2H), 7.00-7.14 (in, 4H), 7.22 (t, lH)57.42(t,2H), 7.51(d,2H) Order---------Line. Printed by the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative

Example 6 0 knot R A

Purification method state: mp ( °C ) RB -CH3 chromatography (hexane white solid -150- This paper scale applies to China National Standard (CNS) A4 specification (210 297 297 mm) 1295281 A7 B7 V. Description of invention ( A): Methyl chloride 1 0 1 - 1 0 3 substance = 1 : 1) ' (Please read the back note and fill out this page) 1 H-NMR [5 (ppm)] : 3.25 (s, 3H ), 7.23(d,2H) , 7.3 7 - 7.5 8 ( πι, 7H) Example 6 1 Structure Purification Method Status: mp ( °C )

RARB c8h17o-^_ -CH3 Chromatography (hexane white solid: ethyl acetate 54-55 = 5:1) Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed 1 H-SMR[5 (ppia)]: 0.90 (t , 3H), 1.22-1.40 (in, 8H), 1.40-1.52U, 2H), 1.83U, 2H), 3.27 (s, 3H), 4.00 (t, 2H), 6.98 (d, 2H), 7· 54(d, 2H) Example 6 2 Structure purification method Status: mp ( °C )

R A R B -151- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. Invention description (W)

CH3 chromatography (hexane yellow liquid: ethyl acetate = 6:1) 1 H-NMR [S (ppi)]: 3.25 (s, 3H), 4.05 (s, 2H), 7.18-7.35 (m, 7 Η) ), 7 · 4 5 ( d, 2 Η ) Example 6 3 Structure purification method State: mp ( ° C ) RARB c8h17 〇 H 〇 > - - C3 H7 chromatography (hexane colorless liquid: ethyl acetate = 9: 1) (Please read the notes on the back and fill out this page) --------Book -------I · 齐% !才匚Η fiL· 1 H-NMR[0' (ρρπι ) ] : : Ο . 89 (t , 3H) , 1 . 1 1 (t , 3H) , 1 . 2 4 - 1 . 4 0 ( ιη, 8Η) 51·41-1·52(ιη, 2Η), 1 · 80 (πι, 2Η), 1.94 (πι, 2Η), 3.39 ( t, 2 Η ·), 4 · Ο 0 (t, 3 Η ), 6 · 9 8 ( d, 2 Η ), 7 · 5 3 ( d,2 Η ) Example 6 4 152 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. Description of invention (4) Structure purification method Status: mp ( °C )

RARB (Please read the note on the back page below) ^h9〇h0&gt;- -CHs Recrystallized from 2-propanol white solid 52-53 1 H-NMR[5 (ppm) ] : 0 . 99 ( t , 3H) , 1. 51 (in, 2H) , 1. 79 (ia, 2H), 3.26 (s, 3H), 4, 03 (t, 2H), 6.98 (d, 2H), 7.53 (d, 2H) Example 6 5 Structure purification method Status: mp ( °C )

RARB Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed - C3 H7 Chromatography (hexane light yellow liquid: ethyl acetate = 5:1) 1 H-NMR [(5 (ppm) ] : 0 . 98 (t , 3H ), 1 .1〇(t , 3H) , 1. 49 (κι, 2H), 1.78 (ra, 2H), 1.92 (m, 2H), 3.38 (t, 2H), 4.02 (t, 2H), 6.98 ( d, 2H), 7.52 (d, 2H) -1 5 3 - This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 Α7 Β7 V. Invention description (π)

Example 6 6 knot R A structure

R

Purification method state: mp ( ° C , 〇 , , (Τ C3 H7 recrystallized from ethanol white solid 98 1 H-NMR [0N (ppm) ] : 1 . 11 (t , 3H) , 1. 92 (m , 2H) , 3 . 39 (t , 2H), 4. 32 (m, 4 Η), 6.97 ( , lfl) , 7. 05 (m, 2H)

Example 6 7 knot R A structure

R (Please read the note on the back and fill out this page) Purification Method Status: mp ( °C ) — — — — — — — — — — — — — — — — - Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed Ύτ -c3 η7 chromatography (hexane yellow liquid: ethyl acetate = 5:1) 1 H-NMR [(5 (ppm) ] : 1 . 12 (t , 3H) , 1. 98 (hi, 2H) , 3 , 45 (t , 2H), -154- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. Invention description (v5\ • 2 2 - 7 · 2 7 U , 1 Η ),7 · 7 7 - 7 · 8 5 ( m,2 Η ) Example 6 8

Purification method Status: m p ( °C

R

R CH h3oc.h C12H25 Shibuya C3 H7 chromatography (hexane yellow liquid: ethyl acetate = 20:1) 1 Η-ΝΗΕ [ δ (ppm) ] : 0 . 88 (t , 3 Η ) , 1 . 12 ( t , 3Η) , 1 . 18-1 . 43 (in 22Η),1·44·1·53(πι,2Η),1·83(πι,2Η),1·95(ιβ,2Η),3· 28-3.42 (ffl, 3H), 4.01 (t, 2H), 6.84-6.90 (itt, lH), 7.38-7.42 (i, 2Η) (Please read the notes on the back and fill out this page) -BUB IBM μ ·· ϋΒ··· am I aam 一-°J· ϋ 1 I 1 i ·1 n I · Printed by the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative

Example 6 9 knot R A

Purification method state: mp ( °C ) RB C3 H7 chromatography (hexane: ethyl acetate = 3:1) 155- colorless liquid This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 Δ7 A7 ___B7_____ V. Description of invention (ίίΓ&gt;) 1 tt-NMR [5 (ppm) ] : 1 . 10 (t-, 3H) , 1. 27 (t , 3H) , 1. 92 (in, 2H) , 2 . 8 2 (t , 2 H ) , 3 . 3 9 (t , 2 H ) , 4 . 2 0 ( q , 2 H ) , 4 . 3 0 ( m . 4 H ) , 7 . 0 2 ( d , 2 H ) , 7 . 5 1 ( d , 2 H ) Example 7 0 Structure purification method Status: mp (°C) Ra Rb ? jTY c2h5ct,, 2) 2-〇人^-c3h7 Chromatography (hexane : ethyl acetate 3:1) colorless liquid 38-40 1 · 10(t,3H), 1.27(t,3H), 1.92(m,2H), 2.82(t,2H), 3.39(t,2H), 4.20(q,2H), 4.30(m,4H), 7.02(d,2H),7.51(d,2H)

Spring Example 7 1 Structure Purification Method Status: m p ( °C ) R A R B c16h33〇

C3 h7 chromatography (hexane white solid: ethyl acetate 38-40 = 13:1) (Please read the notes on the back and fill out this page)

Order · Line · Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1 H-NMR [5 (ppm)]: 0.88 (t > 3H), 1.10 (t, 3H), 1.22-1.42 (in, 24Η), 1.42 »1.53(ια,2Η), 1.78-1.88(ια,2Η), 1.88-1.98(ιιι, 2H), 2.25(s,3H), 3.38(t,2H),4.02(t,2H),6.88(d ,lH), 7 · 32(s,1H) , 7·40(d, 1H)

S example 7 2 structure R A R

Purification method Status: m p ( °C 156 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7

V. Description of the invention (A c, 2h25o

C3 H7 chromatography (methylene yellowish liquid chloride = 5:1) 1 H-NMR [5 (ρρι)]: 〇.89 (t, 3H), 1.12 (t, 3H), 1.20-1.41 (a, 16H), 1.42-1.53 (ffl, 2H), 1.83 (in, 2H), 1.94 (ina2H), 2.24 (s, 3H), 3.40 (t, 2H), 4.01 (t, 2H), 6.87 (d, lH) ), 7.33 (s, lH), 7.40 (d, 1H)

Spring Example 7 3 Structure RAR Purification Method Status: mp ( Ό ) ο C3H7-!-〇Ο ^〇^ry- -c3 h7 Recrystallized from Ethanol White Solid 73-74 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1 H-SMR[S (ppm) ] : 1 . 08-1 . 18 (ϊβ , 6H) , 1. 94 (in, 2H) , 2 . 07 (m, 2 Η ), 3 · 3 2 (2 Η ) ,3 · 4 0 (t,2 Η ),6 · 9 4 ( d , 2 Η ),7 · 5 7 ( d,2 Η ) -157- (Please read the notes on the back and fill out this page)

This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7

B7_5, invention description (Μ) Example 7 4 Structure purification method State: m ρ ( °C ) RARB -C3 H7 chromatography (hexane yellow solid: ethyl acetate 105 = 3:1) 1 H-NMR [a (ppni)]: 1.08 (t, 3H), 1.90 (in, 2H), 3.04 (s, 6H), 3.38 (t, 2H), 6.89 (d, 2H), 7.58 (d, 2H)

Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed I I I compound, R i is R 2 is F ; R 3 / is h3c, -1 5 8 - (please read the back note and fill out this page)

This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. Description of the invention (π) The compound of Example 7 5 may be 2 molar relative enthalpy and 1 molar relative chloride. Prepared according to the method of Example 1-2, this compound was purified by recrystallization from methanol, and was white solid, m.p. 135 - 137. [M]: </ RTI> </ RTI> </ RTI> </ RTI> ;1,4Η) , 7*39(d,4H), 7,88(t,lH) , 8.36(d,2H), 8 · 6 3 ( s , 1 H ). Example 7 6 : .Λ ,S,, 々 (Please read the note on the back and fill out this page) -Ο, f3c 〇CH3 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed I I I compound, R i is h3C\‘

The compound of Example VII can be prepared from a 2 molar relative oxime and a 1 molar relative chloride according to the procedure of Example 1-2. This compound is recrystallized from ethanol and is a white solid, m.p. 1 2 81C. AH — NMR Selling Material [ppm] : 3*88(s,6H), -159- This paper size is applicable to China National Standard (CNS) A4 Specification (210 X 297 mm) 1295281 Α7 Β7 V. Invention Description (τ5ο 6 -98 (d,4H) ,7,47 (d,4H), 7*87(t,lH) ,8.35(d,2H), 8 ♦ 6 2 ( s,1 H ) 〇Example 7 7 : C3H7〇 2S—〇一 IM W f3c o S,) 2-S〇^C, cr n—〇一s〇2c3h7 (please read the notes on the back and fill out this page)

a compound of formula I I, R is

R

Is F; R3 is a S〇2C3H order--------- line. Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative prints examples 7 7 compounds can be 1 molar relative bismuth and 2 mur relative Chloride, prepared according to the procedure of Example 1 ♦ 2, was recrystallized from methanol and was white solid, m.p. 84 - 86. 1 Η — NMR data [ppm]: 1 · 1 1 ( t , 6 Η :) , 1·93 (πι, 4Η), 3, 24 (s, 4H), 3*40 (t, 4H), 7, 37(d,4H), 7 · 4 4 ( d ,4 H ) 〇-160 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. Invention description (β) Example 78 : 2,2 , 2 -trifluoro-l-(4-methoxyphenyl)-ethanone oxime- 0-(1-propylsulfonate) (Ε-, Ζ-isomer mixture) 78 ·1:2,2,2-trifluoro-l-(4-methoxyphenyl)-ethanone oxime (Ε-, oxime-mixture of isomers) 10 g (49·〇 mmol) 2 '2,2-trifluoro-l-(4-methoxyphenyl)-ethanone was dissolved in 100 ml of ethanol, and 4 ♦ 1 g (5 8 ♦ 8 mmol) was added to the solution. Hydroxyl ammonium chloride and 1 1 ♦ 9 ml (1 4 7 mM) of pyridinium. The reaction mixture was heated under reflux for 4 hours, and the solvent was distilled off with a rotary evaporator. The residue was poured into 50 ml of water and extracted with 1 mL of EtOAc and 50 mL of ethyl acetate. The organic phase was washed with aqueous potassium hydrogen sulfate, water and brine, dried (MgSO.sub.4) and concentrated. The residue was purified by chromatography on silica gel, and the eluting agent was methyl chloride to obtain 5.3 g of 2,2,2-trifluoro-l-(4-methoxyphenyl)-ethanone oxime. It is a white solid with a melting point of 62 - 80 °C. The structure was determined by 1H-NMR spectroscopy: (CDC 1 3 ) 0 δ [ppm] : 3,84 (s, 3H) 6*93 (Ε) / 6*99 (Z) (d, 2H), 7·45 ( Ε)/7·55(Ζ) (d, 2H), 8*78 (brs, lH) 0 The absorption signal is determined to be the E- and Z-configuration. The spectrum shows that this compound is a mixture of E- and Z-isomers, and the ratio of E:Z mixture is estimated to be 1: 1 〇-1 6 1 - This paper scale applies to China National Standard (CNS) A4 specification (210 X 297) () Please read the note on the back and fill out this page. Order---------Line· Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1295281 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed V. V. INSTRUCTIONS (J) 78.2: 2,2,2 -Trifluoro-1 -(4-methoxyphenyl)-Ethyl ketone oxime- 0 (1 propyl sulfonate) · (Heterogeneous Mixture 3) 7 ♦ 7 g (1 7 · 0 mmol) of 2, 2, 2 - trifluoro-1 (4-methoxyphenyl)-ethanone oxime (isomer mixture) dissolved in 2 0 ml of THF and cooled in an ice bath: ' Add 2 ♦ 7 g (1 8 ♦ 7 mmol) of 1-propane sulfonium chloride to this solution, then add as droplets 3 ♦ 6 ml (2 5 · 5 mmol) of triethylamine, the reaction mixture was stirred at 0 ° C for 1 hour, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried (MgSO4) and concentrated. 2, 2 - Trifluoro- 1 -(4-methoxyphenyl)-ethanone oxime - (1 -propyl sulfonate), which is a pale yellow liquid. The structure was determined by 1H-NMR spectroscopy: (CDC13) [ppm] : 1,11 (t, 3 Η ) , 1. 88 — 2.02 (m, 2H) , 3·34 - 3.43 (m, 2H) , 3*88 (s,3H), 6*95-7*03 (m&gt;2H) ^ 7 * 5 2-7· 58 (m,2 H ) The 〇 spectrum shows that this compound is a mixture of E- and Z-isomers. . Example 79: 2,2,2-trifluoro-l-(4-methoxyphenyl)-ethanone oxime-o-(1-propyl sulfonate) (single isomer) 79 · 1 : 2 , 2,2 -Trifluoro-1 - (4-methoxyphenyl) -162- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) ' &quot; ------ --------------- Order --------- Line · (Please read the notes on the back and fill out this page) 1295281 A7 B7 V. Description of invention (d) One Ethyl Ketone (Single Isomer) (Please read the note on the back to write this page) 1 1 8 ♦ 5兎(〇♦ 5 8m) 2,2,2—Trifluoro—(4 — A Oxyphenyl) Ethyl bromide is dissolved in 470 ml of ethanol and heated at 80 ° C. This solution is added to a solution of 4 2 * 4 g in 2 4 ml of water (0 · 6 1 moles of ® _ chloride and 8 0 · 9 grams (〇 · 9 9 moles) of sodium acetate. The reaction mixture was heated under reflux for 5 hours, and &lt;a rotary evaporator was evaporated to give a solvent. The residue was poured into water (500 ml). The solid was isolated by filtration and recrystallized from toluene to give 7 3 · 1 g of 2' 2' 2 -trifluoro-(4-methoxyphenyl)-ethanone oxime as a white solid. The structure was determined by 1 Η NMR spectroscopy: (C D C 1 3 ). d [ppm] : 3·84 ( s » 3 Η ) , 6, 99 (d, 2 Η ) , 7, 55 (d, 2H) , 9 * ll (br s, 1 H ). The spectrum shows that this compound is a single isomer ' and is Z-configuration 0 79. 2: 2,2,2 -trifluoro-l-(4-methoxyphenyl)-e-ketoneoxime- 0 — (1 Monopropyl sulfonate) (single isomer) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 12 · 0 g (54 · 8 millimoles) of 2, 2, 2 - trifluoro-1 (4 Methoxyphenyl)-ethanone oxime (single isomer) was dissolved in 100 mL of THF and cooled in an ice bath. To this solution was added 9 * 4 g (65 · 7 mmol) of 1-propanesulfonium chloride, followed by the addition of 8 ♦ 3 g (82 ♦ 1 mmol) of triethylamine. Stir the reaction mixture at 0 Torr for 1 hour and pour into ice water -1 6 3 - This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mil). A '1295281 Α7 _ Β7 V. Invention description u. ), and W ethyl acetate extraction. Wash with organic cypress κ water and brine, dry ((Please read the note on the back to write this page) M g S 0 4 ) and concentrate, the residue is purified by methyl chloride chromatography to obtain 1 5 ♦ 8 g ( 4 8 ♦ 6 mM; 8 9 %) of 2,2,2-trifluoro-l-(4-methoxyphenyl)-ethanone oxime-one (1-propyl sulfonate), It is a pale yellow liquid. The structure was determined by 1 Η-NMR spectroscopy: (CDCI3). 5 [ppm] *1*11 ( t

, 3H), l*94(m, 2H), 3*39(t, 2hT), 3.88(s, 3H), 7.00(d, 2H), 7*54 (d, 2H). The spectrum shows that this compound is a single isomer and is in the Z-configuration. Example 80: 2,2,2-trifluoro-l-(4-phenoxyphenyl)-ethanone ketone-o-(1-propylsulfonate) (E-, Z-isomer mixture) 80 · 1 : 2,2,2 -trifluoro-l-(4-phenoxyphenyl)-ethanone oxime (E-,Z-mixture of isomers) Printed by the Intellectual Property Office of the Ministry of Economic Affairs 122 g (0 '46 mol) of 2,2,2-trifluoro-l-(4-phenoxyphenyl)-ethanone was dissolved in 370 ml of ethanol at a temperature of 80 ° C. 3 3 · 3 g (0 ♦ 4 8 mol) of hydroxyammonium chloride and 6 3 · 7 g (0.77 mol) of sodium acetate dissolved in 1 90 ml of water were added. The reaction mixture was heated under reflux for 5 hours, and poured into water to precipitate a pale yellow solid. The precipitate is filtered off, washed with water and added to hexane, and applied to China National Standard (CNS) A4 specification (210 X 297 mm) at 6〇-16 4-sheet scale. Ministry of Economic Affairs Intellectual Property Office staff Consumer Cooperatives Printed 1295281 A7 B7 V. Inventive Note (w) Heating at 0 ° for 20 minutes, after cooling &gt; Separation of solid 9 K hexane washing y can obtain 1 〇 9 g of 2 f 2 f 2 — trifluoro — 1 ( 4 —Phenoxyphenyl) — ethyl hydrazine> It is a white solid 0. The structure is determined by 1 Η — N Μ R spectrum ϊ ( CDC 1 3 ) 0 δ r LP Ρ m ] : 7 ♦ 〇 〇— 7 * 1 0 ( m 4 Η ) 7 ♦ 1 8 ( tj 1 Η ) y 7 ♦ 3 9 ( t &gt; 2 Η ) , 7 ♦ 5 5 ( d &gt; 2 Η ) 9 9 • 3 5 ( b Γ s 1 Η ) 〇8 〇• 2 * 2 9 2 9 2 trifluoro 1 -( 4 -phenoxyphenyl) 1-ethanone oxime - oxime (1 -propyl sulfonate) Mixture of 1 0 g (3 5 • 6 mmol) of 2 9 2 9 2 trifluoro- 1 - ( 4 - phenoxy) Acetyl (isomer) is dissolved in 7 mL of T Η F and cooled in an ice bath. 0 Add 1 ♦ 2 g (5 0 ♦ 2 mM) of 1 C to this solution. The sulfonium chloride was burned, and then 6 ♦ 3 g (6 2 ♦ 7 mmol) of triethylamine was added to the reaction mixture at 0 V for 1 hour. 9 Pour into ice water and extract with ethyl acetate. 0 has a healthy m phase Κ water and brine wash $ dry lUS; ( Μ SS 0 4 ) and concentrated 9 residue K hexane / ethyl acetate ( 5 : 1 ) chromatographic purification f can get 8 ♦ gram (2 〇 ♦ 7 millimoles &gt; 5 8 % ) 2 2 f 2 trifluoro-1 - (4-phenoxy) ketone oxime - (1 - propyl sulfonate) f white Solid m * Ρ • 4 8 — 5 3 °C 0 The structure is determined by 1 Η - N Μ R spectrum • ( CDC i 3 ) 0 δ CP Ρ m ] • 1 ♦ 0 7 -1 ♦ 1 8 ( m &gt; 3 Η ) 9 1 ♦ 9 2 ( Ζ ) / 2 1 〇( E ) ( m 9 2 - 165- (Please read the note on the back and fill out this page) Order---------Line« This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. Invention Description (Heart) Printed by the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative) f 3 ♦ 4 〇( Ζ ) / 3 ♦ 6 7 ( Ε ) ( t , 2 Η ) &gt; 7 * 〇0 — 7 * 1 2 ( mf 4 Η ) , 7 * 1 5 — 7 * 8 ( m 9 1 Η ) 9 7 * 3 4 — 7 ♦ 4 5 ( m &gt; 2 Η ) &gt; 7 * 5 1 ( d % 2 Η 0 The absorption signal is determined as E - and Ζ - configuration 〇 spectrum shows that this compound is an E - and Ζ - mixture of isomers j E : Z The ratio of the mixture is estimated to be 1: 5 0 Example 8 1 : 2 9 2 2 trifluoro- 1 - ( 4 - phenoxyphenyl) - ethyl m 肟 - (1 - propyl sulfonate) (mono-isomer) 8 1 * 1 : 2 f 2 2 - Fluoryl 1-(4-phenoxyphenyl)-ethylene oxime (single isomer) 3 5 g (1 2 4 mM) of 2 &gt; 2 2 —Trifluoro-l-(4-phenoxyphenyl)-ethyl m 肟 (mixture of Ε- and Z-isomers) 5 Example 8 〇♦ 1 Prepared to dissolve in 3 〇 0 ml of the support Chloride in the chloride Add 1 • 1 ml of concentrated C 1 S to the solution and stir at room temperature for 4 ♦ 5 hours 0 reaction mixture 洗涤 water and brine wash dry ( Μ g S 〇 4 ) and concentrate > 3 3 ♦ 4 g of 2 &gt; 2 2 - trifluoro-1 -(4-phenoxyphenyl)-ethanone oxime (single isomer) 9 It is a white solid 0 structure consists of 1 Η - Ν Μ R spectrum determination: ( CDC 1 3 ) 0 δ r LPP m 3 : 7 ♦ 〇〇 — 7 ♦ 1 2 ( mt 4 Η ) t 7 * 1 9 ( t 1 Η ) 7 ♦ 3 9 ( tt 2 Η ) s 8 ♦ 9 5 ( S 9 1 Η ) 0 8 1 • 2 : 2 &gt; 2 2 Trifluoro-1 - (4-phenoxyphenyl) -16 6- Please read the precautions

This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. Invention description (call) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing ~ B_肟一〇一 (1一丙Base acid _) (single isomer) 1 〇• 〇 gram (3 5 • 6 mM) 2 9 2 9 2 fluorodi- 1 —( 4 —phenoxyphenyl)-ethyl m 肟(single-isomer) Dissolved in 8 mL of Ding F and cooled in an ice bath. 0 Add 5 * 6 g (3 9 ♦ 1 mmol) of 1-propane sulfonate to this solution.醯chloride j followed by Μ droplets by adding 5 4 g (5 3 ♦ 3 mmol) of diethylamine 9 The reaction mixture was stirred at 〇 ° C for 1 hour, poured into ice water &gt; and Κ ethyl acetate Extraction 0 The organic phase is washed with water and brine (( SS 0 4 ) and concentrated. The residue is recrystallized from hexane to obtain 1 2 ♦ 6 g (3 2 * 5 mM 9 1 %) of 2 minus 2 9 2 — trifluoro-1 1 (4 Monophenoxyphenyl)-Ethylketone oxime-O-(1-propylsulfonate) It is a white solid 〇 structure determined by 1 Η-N Μ R spectrum • ' ( CDC 1 3 ) 0 δ CP Ρ m ] 1 ♦ 1 1 ( t $ 3 Η ) 9 1 * 9 2 ( my 2 Η ) &gt; 3 ♦ 4 〇 ( t 2 Η ) , 7 ♦ 〇 5 ( d 2 Η ) 9 7 ♦ 1 1 ( d 囔2 Η ) $ 7 * 2 3 ( t , 1 Η ) 9 7 ♦ 4 2 ( t 2 Η ) 7 5 1 ( d $ 2 Η ) 0 The spectrum shows that this compound is a single isomer of $ and is a configuration 0 Example 8 2 : 2 2 2 —trifluoro-1 - ( 4 -dodecyloxyphenyl) 1-ethanone oxime — 0 — (1 propyl sulfonate) ( Ε a $ Z — isomer Mixture) 8 2 ♦ 1 : 2 , 2 9 2 —Trifluoro- 1 1 (4-dodecyloxybenzene-167- (Please read the back of the note first and then fill out this page)

This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumption Cooperative Printed 1295281 A7 B7 V. Invention Description (#) Base) One B_肟 (E —, Z - a mixture of isomers) 32 g (89 · 3 mmol) of 2,2 , 2 -trifluoro-1 - (tetradodecyloxyphenyl) monoethyl ketone dissolved in 200 ml In ethanol, 7.4 g (107 mM) of hydroxyammonium chloride and 2 1 · 2 g (268 mM) of pyridine were added to the solution. The reaction mixture was heated under reflux for 1 hour and the solvent was distilled off from a rotary evaporator. The residue was poured into water and extracted with ethyl acetate. The organic phase was washed with aqueous potassium hydrogensulfate solution, water and brine, dried (MgSO.sub.4) and concentrated. The residue is recrystallized from hexane/toluene to give 8 ♦ 4 g of 2,2,2-trifluoro-l-(4-dodecyloxyphenyl)-ethanone oxime as a white solid. 70 - 72 °C. The structure is determined by 1 Η NMR spectroscopy: (CDC 1 3 ) 0 δ [ppm] : 0,89 (t, 3H), 1 *20~1 - 40 (m* 16H) , 1.4〇1·50 ( Ιη,2Η) » 1 *79 ( m ^ 2 Η ), 3·86 - 4·03 (γπ, 2Η), 6.93 (Ε) / 6.97 (Ζ) (d, 2H), 7*44 (Ε ) / 7·53 (Ζ) (d, 2H), 8·59 (Ζ) / 8·61 (Ε) (br 3, 1^). The absorption signal is determined to be £1 and Ζ-configuration. The spectrum shows that the compound is a mixture of hydrazine- and hydrazine-isomers, and the ratio of the E: hydrazine mixture is estimated to be 1:4. 82.2: 2,2,2 -trifluoro-l-(4-dodecyloxyphenyl)ethanone oxime-(1-propylsulfonate) (mixture of hydrazine- and hydrazine-isomers) ) -168- This paper size applies to China National Standard (CNS) A4 specification (2.10 X 297 public love ^ (please read the back of the note first and then fill out this page)

1295281 A7 B7 V. INSTRUCTIONS 〇 6〇 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 8 • 〇克 ( 2 1 * 4 1 — ( 4 — 12 alkoxy benzene mixture) dissolved in 5 〇 ml £P 0 Add 3 ♦ propane to dilute chloride in this solution> Next Μ 3 2 ♦ 1 mM) Triethyl hour 9 Pour into ice water 9 and Μ Wash and dry ( Μ SS 〇 Crystal &gt; Available 9 • 1 gram ( 1 2 &gt; 2 - difluoro - 1 - ( 4 0 - 1 - propyl acrylate) - 4 1 °c 0 The structure consists of 1 Η — ) 0 δ C Ρ P m ] : 0 ♦ t , 3 Η ) 1 ♦ 2 〇 — 1 ♦ 4 〇 — 1 * 5 0 ( m ( m 2 Η ) &gt; 1 ♦ 8 7 3 ♦ 3 2 a 3 • 4 2 ( m ) 1 6 * 9 3 — 7 ♦ 〇〇7 • 5 7 ( m 9 2 Η ) 0 — a mixture of isomers 0 Example 8 3 1 2 9 2 &gt; 2 a base) A ym moon bow — 〇 1 (1 mM) 2,2,2-trifluoro-yl)-ethanone oxime (E- and Z-isomeric THF, and it is cooled in an ice bath 4 g (23 + 6 mmol) 1 Add 3 ♦ 3 g (amine, stir the reaction mixture at 0 ° C 1 ethyl acetate extraction, organic phase water and salt 4 ) and concentrate, the residue from methanol in 9.0 mM; 89%) of 2,dodecyloxyphenyl)-ethanone oxime, which is a white solid, determined by m·ρ·40 NMR spectroscopy: (CDC13 8 8 ( t,3 Η ) , 1 · 1 Ο ( 1 ♦ 4 Ο ( m,1 6 Η ), , 2Η), 1*75-1,85 a 1 ♦ 9 8 ( m,2 Η ),

, 2Η), 4,00(t, 2H (m, 2H), 7*48- spectrum shows that the compound is mono- and Ζ trifluoro-l-(4-dodecanoxybenzene-propyl sulfonic acid Ester) (single isomer) -169- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page) ------ —订---------- · 1295281 7 Α7 Β7 5, invention description 8 3 ♦ 1 : 2 , 2, 2 -trifluoro- 1~(4-dodecyloxyphenyl)-B嗣肟 (single isomer) 15 g (41 · 8 mmol) of 2,2,2-trifluoro-}(4-dodecyloxyphenyl)-ethyl hydrazine dissolved in 1 〇〇 ml In the ethanol, a solution of 3,5 g (5 0 ♦ 2 mmol) of the quaternary ammonium chloride and 1 〇·1 ml (1 2 5 · 4 mmol) is added to the solution. The reaction mixture was heated under reflux for 2 hours, and the solvent was distilled off with a rotary evaporator. The residue was poured into water (100 ml), then 1 〇 0 ml, and then extracted with 50 ml of ethyl acetate. Wash with aqueous potassium hydrogen sulfate, water and brine, and M g S 0 4 ) dried and concentrated. The residue was dissolved in 1 mL of methyl chloride chloride' and 4 2 g of concentrated HC 1 was added to the solution. The reaction mixture was stirred at room temperature overnight, and Pour into the water. After removing the aqueous phase, the organic phase is washed with water and brine, dried (MgS〇4) and concentrated. The residue is recrystallized from hexane to give 9 ♦ 7 g of 2, 2, 2 — Trifluoro-1(4-dodecyloxyphenyl)-ethanone oxime, which is a white solid, p ♦ 75 - 76. C. The structure is determined by iH-NMR spectroscopy: (CDC13) ύ δ [ppm] *0*89 (t'3H) '1*21 — 1·4〇—1·52(γπ, 2Η) , 1·80(γπ, 2Η ), 3·99&quot;, 2Η) , 6.97 (d, 2H ), 7 ♦ 5 3 ( d, 2 Η ) , 8 ♦ 4 3 ( s, 1 Η ). The spectrum shows that the compound is a single isomer and is in the oxime configuration. When sulfuric acid is used instead of HC 1 , 2,2,2-trifluoro- 1 - 1 7 0 - is also available. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm). (Please read the note on the back first? Then fill out this page) Order---------Line - Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1292851 A7 B7 V. Invention Description (w) Ministry of Economic Affairs Printed by the Intellectual Property Office Staff Consumer Cooperative (4 - Dodecyloxyphenyl) 1-Ethyl Ketone 8 0 8 3 ♦ 2 : 2 2 9 2 — Difluoro- 1 - '( 4 -12 oxyphenyl) ) 乙 肟 肟 — 0 — ( 1 propyl sulfonate) (single isomer) 7 ♦ 〇 (1 8 ♦ 7 mM) 2 2 &gt; 2 — Difluoro — 1 (4) —dodecyloxyphenyl)-i-i-isoindole (single isomer) is dissolved in 50 ml of T Η F and cooled in an ice bath 0 2 ♦ 9 g is added to this solution ( 2 〇* 6 millimoles) of 1 - propane sulfonium chloride, followed by Μ droplets by adding 3 9 ml (2 8 ♦ 1 mmol) of diethylamine at 0 °c, mix the reaction mixture for 1 hour, pour into ice water, and pour ethyl acetate to extract ο organic phase Μ water and brine wash 5 dry ( Μ 8 S 〇 4 ) and the concentrated residue are recrystallized from methanol to obtain 7 * 6 g (1 5 • 9 mmoles 8 5 %) of 2 2 2 difluoro- 1 1 (4 12-dodecyloxybenzene) A) m 肟 0 0 ( (1 propyl sulfonate) t which is a white solid 0 structure determined by 1 Η - Ν Μ R spectrum: ( CDC 1 3 ) 0 δ r Ρ P m 〕 0 * 8 8 ( t % 3 Η ) &gt; 1 * 1 0 ( t 9 3 Η ) j 1 ♦ 2 0 — 1 * 4 0 ( m 1 6 Η ) y 1 ♦ 4 0 — 1 * 5 〇( m , 2 Η 9 1 ♦ 8 〇( m 9 2 Η ) 1 ♦ 9 4 ( m 2 Η ) $ 3 ♦ 4 8 ( t &gt; 2 Η ) 9 4 • 〇0 ( t $ 2 Η ) 9 6 * 9 7 ( d 2 Η ) &gt; 7 • 5 3 ( d 9 2 Η ) The 〇 spectrum shows that this compound is mono-isomer f and is Ζ one configuration 0 Example 8 4 , 2 &gt; 2 2 Difluoro 1 ( 4 hexadecane phenyl hydrazine 71- (please read the notes on the back and fill out this page)

This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 Α7 Β7 V. Inventive Note (4) Base) Ethyl ketone head bow 0 — (1 propyl acrylate) (E -, Z - a mixture of isomers) 84· 1:2,2,2—trifluoro-1(4-hexadecyloxyphenyl)-ethanone oxime (E-, Z-isomer Mixture) 27 g (65·1 mmol) of 2,2,2-trifluoro-l-(4-hexadecyloxyphenyl)-e-one in 100 ml of ethanol in this solution 4 · 5 g (65 · 1 mmol) of hydroxyammonium chloride and 1 2 ♦ 9 g (1 63 3 mmol) of pyridine were added. The reaction mixture was heated under reflux for 4 hours and the solvent was distilled from a rotary evaporator. The residue was poured into water and extracted with ethyl acetate. The organic phase was washed with aqueous potassium hydrogensulfate solution, water and brine, dried (MgSO4) and concentrated. The residue is recrystallized from hexane/toluene to give 1 3 · 5 g of 2,2,2-trifluoro- 1 -(tetrahexadecyloxyphenyl)-ethyl hydrazine, which is ash Twilight solid, 76 — 80t:. The structure was determined by 1 H-NMR spectroscopy: (C D C 1 3 ). δ [ppm] : 0 ♦ 8 8 ( t,3 Η ) ,i .20 - 1 ‘40 (m,24H) ,1,40 -

l,5 0(m,2H) ,1·75 - l,84(m,2H ),3·96— 4.02 (m,2H) ,6·89 ( Ε ) /6·95(Ζ) (d, 2H) , 7·43(Ε)/ 7 · 5 2 ( Ζ ) (d, 2H) , 8, 28 (Ζ) / 8 ♦ 4 3 ( Ε ) ( brs , 1 Η ). The absorption signal is determined to be Ε一 and Ζ-configuration. The spectrum shows that the compound is a mixture of hydrazine- and hydrazine-isomers, and the ratio of the E: hydrazine mixture is estimated to be 7:3. -172- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the note on the back and fill out this page). Order---------Line - Ministry of Economics Property Bureau Staff Consumer Cooperative Printed 1295281 A7 B7 V. Description of Invention (Μ) 8 4 * 2 : 2,2,2 -Trifluoro-1(4hexadecyloxyphenyl)Ethylquinone# (1 -propyl sulfonate oxime (E - and Z - a mixture of isomers) 8 ♦ 0 g (18 ♦ 6 mmol) of 2,2,2 -trifluoro- 1 - (4-16 Alkoxyphenyl)-ethanone oxime (E- and Z-isomer mixture) was dissolved in 50 mL of THF and cooled in an ice bath. 2,9 g (2) was added to this solution. 0 ♦ 5 mM) of 1-propane sulfonium chloride, followed by hydrazine dropwise addition of 2 · 8 g ( 2 7 * 9 mmol) of triethylamine, stirring the reaction mixture at 〇 ° C In an hour, it is poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried (M g S 0 4 ) and concentrated, and the residue is recrystallized from methanol to obtain 8 ♦ 9 g (1 6 · 6 millimoles; 8 9 % ) 2, 2,2 -trifluoro-1(4-hexadecyloxyphenyl)-ethanone oxime (1 propyl sulfonate), which is a white solid, γπ·ρ·56 — 5 7 ° C. The structure is determined by 1 Η NMR spectroscopy: (CDC i 3 )0 δ [ppm] *0*88 (t,3H) ? 1*12 ( t,3H) ,1*18—1*40 (m,24H), 1·40-1·5〇(ιη,2Η) , 1,76— 1,85 (m,2H) ,1·88 — 2*〇2(m,2hT),

3,32 — 3·44 (m,2H) ,4·02 (t,2H ),6*93 - 7,00 (m,2H) ,7·48 —

7 ♦ 5 6 ( m, 2 H ). The spectrum shows that this compound is a mixture of E- and Z-isomers. -173- ------------- (Please read the notes on the back and fill out this page) Order---------Line; Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 _____ B7____ V. Invention Description (W) Example 85: 2,2,2 -Trifluoro-1 1 (4-16 Alkoxyphenyl)-ethoxime-0-(1-propylsulfonate) (single isomer) 85· 1 :2,2,. 2 —trifluoro-l-(4-hexadecane) Oxyphenyl) ethyl ketone oxime (single isomer) 5 ♦ 3 g (1 2 ♦ 3 mmol) of 2,2,2-trifluoro-l-(4-hexadecyloxyphenyl) Ethyl ketone oxime (a mixture of ruthenium and osmium-isomers) (prepared according to the method described in Rex. 8.4) was dissolved in 100 ml of methyl chloride. To this solution was added 1 ♦ 〇 ml of concentrated H C 1 and stirred at room temperature overnight. The reaction mixture is washed with water and brine, dried (MSS 0 4 ) and concentrated to give 5.3 g of 2, 2,2-trifluoro-l-(4-hexyloxyphenyl)-B- Bow (single isomer) which is a white solid, m.p.: 84- </RTI> The structure was determined by iH-NMR spectroscopy: (CDC13), δ [ppm]: 0*88 (t, 3H) - 1 · 40 (m, 24H), 1 , 40 - 1 · 5 〇 (m, 2 Η ), l*80(m,2H),4,0〇(t,2H) Printed by the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative, 6.95(d,2H), 7*52(d,2H), 8-06 ( s » 1 H ). The spectrum shows that this compound is a mono-isomer and is in the Z-configuration. 85*2: 2,2,2-trifluoro-l-(4-hexadecyloxyphenyl)-ethanone oxime- 0-(1-propyl sulfonate) (single isomer) 5 ♦ 2 g (1 2 · 2 mmol) of 2,2, trifluoro- -174- This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. Invention description (" 7〇1 one (4-16 in 50 0 into 1 ♦ 9 followed by liquid triethylamine, and Μ acetic acid M g S 0 liter of T gram (1 drop of square at 0 〇c 乙i extract 4) And 5 ♦ 8 g (10 0 fluoro-l-(4-propyl sulfonate), the structure consists of 1 Η — N δ [ppm] : alkoxyphenyl HF, and 3 ♦ 3 mM is added to 1 ♦ Stir the reaction. The organic phase is concentrated and the residue is ♦ 8 mM hexadecyloxy group. The white solid MR spectrum is 8 8 ( 3 Η ), 1 · 5 1 · 2 0 ( m (m, ( t, (d , 3 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1 · 9 3 4 ♦ 〇 2 7 * 53 , and is Ζ - configuration example 8 6 : , 2 E ), 2 H ) , 3 2 H ), 6 2 H ). Light) monoketone oxime (翚-isomer) is dissolved in an ice bath to cool. a mixture of 1-propanesulfonium chloride, 84 g (18·2 mmol) in the liquid for 1 hour, poured into ice water, washed with water and brine, dried (recrystallized from methanol, purified) Available; 8 9 %) of 2,2,2-triphenyl)-ethanone ketone oxime (1 integral, melting point: 59 - 60 ° C. 定: (CDC 1 3 ), t, 3 Η ) ,:L · 1 2 ( t, 1 (m,24H) ,1*41 1 ♦ 8 0 ( m,2 H ), ♦ 4 〇(t,2 H ), ♦ 9 7 ( d,2 H ), The spectrum shows that this compound is a single isomer (please read the notes on the back and fill out this page). Order --------- Line _

C3H7〇2S—0—N f3c〆&quot;N_0_S〇2C3H7 -175 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 Α7 Β7 V. Invention Description (E- And a mixture of Z-isomers) a compound of formula II; R i 'is -&lt;Q)-〇.(CH2)3-〇hQ&gt;~ R2 is F; R3 is a s〇2 C3 H7 8 6 f3c〆 CF, Example 8 The compound of 6 · 1 is composed of 1 mole of 1 ♦ 3 -diphenoxypropane and 2 moles of 4 - dimethylaminopyridinium, 2 moles of trifluoroacetic acid, and 5 moles. The A 1 C 1 3 of the ear was prepared according to the method of Example 7 ♦ 1. The crude product was recrystallized from toluene. 8 6*2: Please read the back of the note first. This page is printed by the Intellectual Property Office of the Ministry of Economic Affairs.

HO-N W

N-OH /-=\ r=\Η^°'(0Η2)3'0Λ^/°ν (Ε-and Ζ-mixture of isomers) Example of 8·0 g (42·8 mmol) 86·1合合-176- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed A7 B7 V. Invention description (W) Dissolved in 1 In 0 ml of ethanol, 6 ♦ 0 g (85 ♦ 7 mmol) of ammonium hydroxychloride and 1 S ♦ 9 g (2 1 4 mmol) of pyridinium were added to the solution. The reaction mixture was heated under reflux for 4 hours, and the solvent was distilled off with a rotary evaporator. The residue was poured into water and extracted with ethyl acetate. The organic phase is washed with an aqueous solution of potassium hydrogensulfate, water and brine, dried (M g S 〇 4 ) and concentrated, and the residue is purified by recrystallization from toluene to give 1 6 ♦ 1 g of the compound of Example 8.6. It is a white solid. The structure is made up of 114 one ~? 41^Spectrum (0Bu150—(1(5) confirmed. δ [ppm] : 2*22-2 *34 (m'2H) ' 4.22 - 4·32(πι,4Η) , 7* 0 6 — 7.17 (m, 4H), 7·47/7·52 (d, 4H). This spectrum shows that this compound is a mixture of E- and Z-isomers. 8 6*3: c3h7o2s-〇-n /=v / =\ //n-〇-s〇2c3h7 (E- and Z-isomer mixture) 8·0 g (17♦8 mmol) of compound 86♦2 (E- and Z-isomer The mixture was dissolved in 80 ml of THF and cooled in an ice bath. 5 ♦ 6 g (3 9 · 1 mmol) of propane sulfonium chloride was added to the solution, followed by hydrazine droplets. Way to add 5,4 grams (53 ♦ 3 millimoles) of triethylamine 'stirred at 〇 ° C anti-177- This paper scale applies to China National Standard (CNS) A4 specifications (210 X 297 mm) - ------------·1丨丨-丨-丨定---------Line Up . (Please read the notes on the back and fill out this page) 295281 A7 B7 V , invention instructions () should be the mixture for 2 hours, poured into water, and K ethyl acetate extraction. Wash the organic phase K water and brine, dry (M g S 0 4 ) ' and concentrate, the residue Purification by chromatography (hexane/ethyl acetate: 2:1) afforded 1 0 ♦ 7 g (1 6 ♦ 1 mmol; 9 1 %) of the compound of Example 8.6, which is pale yellow Solid, melting point 80 - 8 4 ° C. The structure is determined by 1 Η NMR spectroscopy: (CDC 1 3 ) δ [ppm]: l, 12 (t, 6H), l, 97 (m, 4H),

2*36 (m,2H) ,3·35 - 3,45 (m,4H ),4*25(t,4H) ,6·98 — 7·〇6(γπ, 4 H ) , 7*54/ 7*58 (d, 4H). The spectrum shows that this compound is a mixture of E- and Z-isomers. Example 8 7 : CF, ------------- (Please read the notes on the back and fill out this page) Order --------- Line · Ministry of Economic Affairs Intellectual Property Bureau employees Printed by consumer cooperatives (single isomers) 8 7

N rz=\ ^N—OH -178 This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. Description of invention (π) (蜇-isomer P m ] : 2 3 0 ( d,4 compound is a single 2 substance soluble

1 2 〇 ear) of evaporation. In organic M g S, the M g S 2 1 · structure at room temperature is determined by δ [ ρ 4 Η ). Spectrum 8 7 * i · Ο 15 0 mM ttli pyridine. Distillation of ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium broth And concentration example 8

N M R 〇* 乙醇 Ethanol based chlorination heat reaction. Residual aqueous solution, residual ruthenium reaction mixture, residual 7 · 1 spectrum ( 4 3 (mole, this ammonium and 2 mixture poured, water and dissolved in •43 compound 由 from the chemical combination DMS m, 2 Η), Example 4 of the isomer) 3 ♦ 8 g of the solution (1 · 5 hours of water, and brine, 150 ml of concentrated water and brine to recrystallize the benzene, which is White 0 - d 6 ) Η ) , 4 ♦ 7 · 7 0 (, which is Ζ - 6 ♦ 1 compound 8 ♦ 4 gram (3 〇〇 imo, and Μ - ethyl citrate extract dried (ethyl acetate C 1 , and in polyester, dry (purified, available color solid. Confirmed. 4 2 ( t, d, 4 Η ) configuration. (Please read the note on the back and fill out this page) Ministry of Economic Affairs Intellectual Property Bureau Printed by employee consumption cooperatives

〇(CH2)3·丨

CFn 0—S〇2C3H7 (single isomer) 8 ♦ 0 g (1 7 · 8 mmol) Example 8 7 · 1 combination -179 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7__ V. Description of the invention (W) The material (single isomer) was dissolved in 80 mL of THF and cooled in an ice bath. 5 ♦ 6 g (3 9, ♦ 1 mmol) of 1-propanol@驴 chloride was added to the solution, followed by droplets of 5 * 4 g (5 3 ♦ 3 mmol) Triethylamine, the reaction mixture was stirred at 〇 π for 2 s. then poured into water and extracted with ethyl acetate. The organic phase is washed with water and brine 'dry (M g S 0 4 ) and concentrated, and the residue is purified by recrystallization from methanol' to obtain 9 ♦ 1 g (1 3 ♦ 7 mmol; 7 7 %) A compound of 7 7 · 2 which is a white solid, m.p. 6 〇 - 6 2 ° C. The structure is determined by 1 Η NMR spectroscopy: (CDC 1 3 δ [ Ρ ρ πι j : l, 12 (t, 6H), 1.97 (γπ, 4Η), 2*36 (m, 2H), 3, 39(t,4H), 4*25(t,4H),7,0 2(d,4H), 7 ♦ 5 3 (d,4 H ) The 〇 spectrum shows that this compound is a single isomer, which is Z - Configuration Example 8 8: - Chemically amplified positive photoresist formulation prepared by mixing the following ingredients to obtain 1 〇 0 ♦ 0 parts of resin binder (2 2 mol% of styrene, 6 9 mol% of bismuth - a copolymer of hydroxy-styrene and 9 mole % tert-butyl acrylate having a M w of 985 〇; RTM Maruzen MARUKA LYNCUR PHS/STY/TBA, supplied by Maruzen Oil, Japan) -180- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the notes on the back and fill out this page). Order---------Line«· Ministry of Economic Affairs Intellectual Property Bureau Employees' Consumption Cooperatives Printed 1295281 A7 B7 V. Invention Description () 0 ♦ 4 parts of leveling agent (FC- 4 30, supplied by 3M) 4〇〇♦ Part of polypropylene glycol methyl ether acetate (PG) Μ EA ) (by Tokyo Kasei, Japan 4) ♦ 0 parts of the test photoacid generator The photoresist formulation K 6 5 0 0 I, rpm is spin-coated onto a ruthenium wafer treated with hexamethyldiindenyl ruthenium, time For 60 seconds, then baking on a hot plate at a temperature of Μ 1 40 ° C for 90 seconds, a film with a thickness of 80 〇nm, and then a deep ultraviolet ray at a wavelength of K 2 5 4 nm, through a narrow Bandwidth interference filter and multi-density quartz reticle, using a Ushio high-pressure mercury lamp ϋΧΜ-5 01 MD exposure photoresist film, and exposure through a mask aligner Canon PLA-521, then a heat On-plate Κ Bake at a temperature of 140 ° C for 90 seconds, followed by imaging. The exposure intensity is measured by Ushio's Uninieter UIT-150, to the required dose for transparency (E 〇), ie at 2 ♦ 3 8 % The immersion of the photoresist film in the tetramethylammonium hydroxide aqueous solution is exactly enough to remove the photoresist film, as described by R. Damniel, Diazonaphthoquinone-based Resists, SPIE Tutorial Text Series Vo 1 T T11, Optical Engineering Press, p. 10-11 (1993) obtained from the inverse curve (characteristic curve). The smaller the dose, the more sensitive the photoresist formulation is; the results are shown in Table 3 and show that the composition is suitable for the preparation of positive photoresists. Table 3: -181- This paper scale applies to the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) (Please read the notes on the back and fill out this page) Order---------Line · Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing [295281 A7 B7 V. Invention description ( w Example compound to transparent dose (E (m J / cm2 ) 2 〇1 8 3 〇1 8 5 〇1 〇6 0 2 3 1 3 1 1 4 1 6 〇1 9 1 7 〇2 4 2 〇0 1 6 2 1 〇1 6 2 6 〇2 5 2 7 〇, 1 5 2 9 〇· &gt; 0 7 (Please read the notes on the back and fill out this page) Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperative Printed Example 8 9 : - Chemically amplified negative photoresist formulation prepared by mixing the following ingredients to obtain 1 〇 0 ♦ 0 parts of resin binder (poly(p-hydroxystyrene) having a molecular weight of 1 1 900; RTM VP-8000, by Nisso , Japan company provides) -182- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 Printed by the Intellectual Property Bureau of the Ministry of Commerce, Consumers' Cooperatives. V. Inventions (/7?) 1 0 ♦ 0 parts of melamine urea resin as crosslinker (N,N-dihydroxymethyl urea, RTiM MX-290, Available from Sanwa Chemical Co., Ltd.) 0 '5 parts of leveling agent (FC-430, supplied by 3M) 7 ♦ 7 parts of photoacid generator (PAG) to be tested 5 () 0 · 〇 Polypropylene glycol methyl ether acetate (PG Μ EA ) (supplied by Tokyo Kasei, Japan) This photoresist formulation was spin-coated at a speed of K 6 0 0 rpm to a K hexamethyl dimethyl hydrazine treatment On the bismuth wafer, the time is 60 seconds, the thickness is 800 nm, and then baked at a temperature of ΚΙ 1 在一 on a vacuum hot plate for 60 seconds to obtain a non-stick photoresist film, and then 2 5 4 η m wavelength source, through a narrow bandwidth interference filter and multi-density quartz reticle, using a Ushio high pressure mercury lamp UXM-501MD exposure photoresist film, and through mask alignre Canon PLA -521 exposure, K assay gel (Gel Dose) (D 〇) (similar to the method of Example 8 8), which is different in light The film is baked for 60 seconds after exposure and immersion in 2 ♦ 3 8 % tetramethylammonium hydroxide aqueous solution, and the gel dose is just enough to leave the crosslinked photoresist film on the substrate after development. The dose on. The inverse curve (characteristic curve) for both positive and negative photoresists is based on gel doses to transparent doses (positive photoresists) and negative photoresists (E·Reichmanis and L.F. Thompson, ACS Syrap. Ser. 412, Polymers in Microlithography, p. 4-5, American Chemical Society, Washington, DC 1989 •183- (Please read the note on the back δ write this page) Install ka· 丨线' This paper size applies to China Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 ___B7_ V. Description of invention (small)), the sensitivity of the resulting negative photoresist is shown in Table 4. Table 4 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed example compound gel dose ( D 〇 ( m J / C m 2 1 〇, 9 6 2 3 ^, 7 4 3 〇 &lt; ►5 7 6 0, ► 4 3 7 1, ►5 〇1 3 3, ►8 1 1 5 〇, ^ 5 2 1 6 0, ' 1 0 1 7 〇' '3 2 2 2 2, ^ 5 8 2 3 1 - 6 5 2 4 〇, 4 2 2 5 2, 5 3 2 6 〇, Ί 9 2 7 〇« 5 7 -1 8 4 - (Please read the notes on the back and fill out this page) Order -------- -Line, the paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1295281 A7 B7 V. Invention Description (w) Example 9 0 : A chemical magnification The resist formulation is prepared by mixing the following ingredients: 1 〇 0 · 0 parts of the resin binder described in Example 8 8 , 0 ♦ 4 8 parts of the leveling agent (FC- 4 3 0, supplied by 3M) 475♦ 0 parts of polypropylene glycol methyl ether acetate (PGMEA) (provided by Tokyo Kasei, Japan) 4 * 0 parts of test photoacid generator Rotating coating of this photoresist formulation M 3 0 0 0 r pm On a ruthenium wafer treated with hexamethylene dimethyl hydrazine, the time is 45 seconds, and then baked at a temperature of 140 ° C for 90 seconds on a hot plate to obtain a thickness of 80 a 0 nm film, then Μ 2 5 4 nm deep ultraviolet light, through a narrow bandwidth interference filter and a multi-density quartz reticle, using a U shi 高压 high pressure mercury lamp UXM-5 01 MD exposure photoresist film, and It was exposed by a mask aligner Canon PLA-521, and then baked on a hot plate at a temperature of 140 ° C and baked for 90 seconds, followed by development. The exposure intensity was Uni Ushio's Unimeter UIT-150 The dose required to measure the transparency (E 〇) is measured by the measured inverse curve, which is just enough to be fully immersed in a 1 ♦ 7 9 % tetramethylammonium hydroxide aqueous solution for 60 seconds. The dose of the light smear film was removed. The smaller the dose, the more sensitive the photoresist formulation was; the results are shown in Table 5 and showed that the composition is suitable for the preparation of positive photoresists. -1 8 5 - This paper scale applies China National Standard (CNS) A4 Specification (210 X 297 mm) --------------------- Order --------- Line · (Please Read the back first Note: Please fill out this page again) 1295281 A7 B7 V. Description of invention (fp) Table 5 Example compound to transparent dose (E 〇(m J / cmz ) Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed 01234 5 678 9 01234567 444444444455 5 5 5 555 1 ♦ 7 9 1 ♦ 6 3 1 * 3 2 1 · 5〇Ο ♦ 9 1 4 · 6 1 Ο ♦ 7 2 4 · 1 6 1 ♦ 6 3 〇· 9 9 1*22 1 *22 〇· 9 9 0*56 0 ♦ 6 9 0*69 1 ♦ 1 7 5*01 -18 6- -------------------- Order -- ------- Line (Please read the note on the back and fill out this page) This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 Ministry of Economic Affairs Intellectual Property Office staff Printed by the Consumer Cooperatives. V. Inventions (w) 5 8 5 9 6 1 6 2 6 3 6 4 6 5 6 6 6 7 6 9 7 0 7 2 7 5 7 6 7 9 8〇8 1 8 3 8 5 8 7 2 ·〇2 1.47 3 ·〇7 1*51 2 ♦ 7 7 2-66 1 · 5 7 2 ♦ 9 0 1 · 1 1 1*33 2*20 4 · 2 5 0*89 1 ♦ 3 0 1 · 2 1 1 ♦ 5 4 1*55 5 ·〇0 7-27 1 ♦ 7 3 (Please read the notes on the back and fill out this page) ---------Book ------ --- Example 9 1 : -187- This paper size is applicable National Standard (CNS) A4 Specification (210 X 297 mm) 1295281 A7 _B7_ V. INSTRUCTIONS (唞) Photolatent acid generating compound in the same amount (by weight) poly(4-hydroxystyrene) (M w = 5 1〇〇, and by Maruzene Oil

Company, Tokyo, Japan, the product of the brand name Maruzene MARUKA LYNCUR PHMC) The degradation point (T d ) in the presence of DSC (Differential Scanning Calorimeter) analysis, the higher the value, the thermal stability of the photolatent acid compound The better the sex, the results are listed in Table 6: (Please read the note on the back and then fill out this page) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed Table 6: Spring Compound T d ( °C ) 1 &gt; 2 0 0 2 &gt; 2 〇〇3 1 8 〇5 1 8 3 6 &gt; 2 〇0 8 &gt; 2 〇〇1 3 1 9 7 1 5 1 7 3 1 6 1 8 6 1 7 1 9 2 1 8 1 7 5 2 〇1 9 6 -188 - Order--------- Line. This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A7 B7 V. Inventions ) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 2 5 1 1 7 6 2 1 8 〇3 2 1 9 5 1 9 7 7 1 8 8 〇1 7 4 1 1 7 〇2 &gt; 2 〇〇3 1 8 5 4 1 8 6 5 1 7 4 6 1 9 8 7 &gt; 2 0 〇8 &gt; 2 〇〇9 1 7 2 〇1 9 3 1 &gt; 2 〇0 2 &gt; 2 0 〇3 1 8 6 4 1 9 〇5 1 8 4 6 &gt; 2 〇〇7 &gt; 2 〇〇-189 (Please read the note on the back and fill out this page) This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) ) Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumers Cooperative, Printed 1295281, 5, Inventions (w) 5 8 5 9 6 1 6 2 6 3 6 4 6 5 6 6 6 7 6 9 7〇7 2 7 5 7 6 7 9 8 〇8 1 8 3 8 5 8 7 A7 B7 &gt;200 19 1 &gt;200 19 3 &gt;200 &gt;200 &gt;200 18 6 18 7 17 3 17 5 &gt;200 17 5 17 5 19 0 18 8 &gt ;200 &gt;200 19 7 18 8 (Please read the notes on the back and fill out this page) ----------Book---------Line 7| Example 9 2 : 190- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm)

Claims (1)

1295281 A8 B8 C8 D8 &quot;―^ t Z5S", Patent Application No. 1. A chemically amplified photoresist composition comprising: (a) a compound which hardens under the action of an acid, or a solubility under the action of an acid Compounds which will be added; and (b) 0 · 1 - 30 weight percent (based on the weight of component (a)) as at least one compound of formula I, II or III, 〇-R3 N II /〇—r3 N /〇N II R (1), Rr II , c\r/R2 hj (ll), 2 R1/c\/2 / XX % (III), where: h is phenyl, which is not a CVC12 alkyl group substituted with or substituted with one or more of the following groups, phenyl-CVCV alkyl, halogen, or4, nr5r6, sr7, s〇r7, and/or so2r7, and optionally substituted Substituting or4, and forming a ring via the r4 group; or fluorenyl is naphthyl or thienyl; R '1 is •A-A-A .......................装------ (Please read the notes on the back and fill out this page) Order #A is -0- Or - S-; A! is Ci-C12 hospital support; Rule 2 is halogen or cvCk haloalkyl; R3 is C:-C18 alkylsulfonyl, q-C1() haloalkylsulfonyl, camphoryl The sulphur paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) A8B8C8D8 1295281 VI. The scope of patent application is thiol, phenylalkylsulfonyl, phenylsulfonyl, naphthylsulfonyl, Wherein the phenyl group on the sulfhydryl group is unsubstituted or substituted by Ci_Ci6 alkyl or 〇r4; R'3 is phenyl disulfonyl, X is fluoro; R4 is phenyl, G-Cu An alkyl group which is unsubstituted or substituted by a c2_Ci2 alkoxycarbonyl group; or R4 is a C1-C18 alkyl group interrupted by one or more _〇_ and which is substituted by a phenyl group Or R4 is CVC18 alkylsulfonyl; R5 and heart are 匕-~alkyl; and 1^7 is phenyl or CVC18 alkyl. 2. The chemically amplified positive photoresist composition of claim 1, comprising = (al) 30-99 weight percent of at least one polymer having an acid labile group, the acid restosting group being in the presence of an acid Decomposing and increasing its solubility in an aqueous alkaline developer solution; and/or (a2) 3-5% by weight of at least one monomer or oligomeric dissolution inhibitor having an acid labyrinth present in the acid Decomposes, thereby increasing the solubility in an aqueous alkaline developer solution; and/or (a3) 60-80% by weight of at least one test-soluble monomer, oligomeric or polymeric compound; wherein the component (al) , the weight ratio of (a2) and (a3) is calculated according to the weight of the component (a) of the first application of the scope of the patent | scope; and.................... ..·装·.............-II................0 (Please read the notes on the back and fill out this page) 1 ___ This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 dongdong) 1295281 A8 B8 C8 D8 VI. Patent application scope (b) 0.1-30% by weight as at least a light sensitive acid supply agent I,1 1 or 111 compound. -----------------------Installation ------ (Please read the notes on the back and fill out this page) 3. If you apply for patent scope A chemically amplified negative photoresist composition of 1 item, including = (a4) 40-99% by weight of alkali-soluble resin as a binder, U5) 0.5-30% by weight when catalyzed by acid and itself And/or a component which produces a crosslinking reaction with the binder, wherein the weight ratio of the components (a4) and (a5) is calculated according to the weight of the component (a) of the first application of the patent scope; and (b) 0.5-15 weight The percentage is regarded as at least one compound of formula I, II or III as a photo-sensitive acid supply. 0 4 · A chemically amplified photoresist composition according to any one of claims 1 to 3, except for components (a) and (b), or components (al), (a2), U3) and (b) ), or components (a4), (a5) and (b), additionally including additive (c), other photo-sensitive acid supply compound (bl), other photoinitiator (d), and/or sensitizer ( e), where the components (a) and (b), (al), (a2), (a3) and (b) and U4), (a5) and (b) are as in the scope of the patent application, l, 2 And those defined in 3 items. 5) A method for preparing a photoresist, which is applied to a substrate by the following preparation (1), as in the first aspect of the patent application; (2) between 60 ° C and 160 ° C Post-baking the composition; __ 3 This paper? Use Chinese National Standard (CNS) A4 specification (210 X 297 GM) 1295281 is, patent application scope (3) Use wavelengths of I50nm and 1500nm light to form an image image -wise) irradiation; (4) selective baking after exposure at a temperature of 60 ° C and 160 ° C; and (5) imaging with a solvent or an aqueous solution of an alkaline developer 6 · For lb, lib or Illb compounds, please read the following notes: η ?-r&quot;3 II(4), CF, R,&quot;; This i "- Page/0-R' /〇Ra 3 N II (Hb), II (Hib) person cf3 /c\ R&quot;&lt; 'CF3 2 2 where: R' is phenyl which is unsubstituted or consists of one or more Q-Cn alkyl, phenylalkyl, Halogen, phenyl, hydrazine R4, NR5R6, SR7, SOR7 and/or S〇2R7 substituted, and optionally substituted with a substituent 〇r4, and via R4 and other on the phenyl ring Substituent group, or a carbon atom and the benzene ring form a ring structure;! ^ Or is naphthyl or thiazolyl group ah (thienyl); R ,,, ^, # This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 public) 1295281 A8 B8 C8 D8 VI. Patent application scope A is -0- or -S-; A! is Q-C12 hospital support; Rn3 Is CVC16 alkylsulfonyl, CVC^ haloalkylsulfonyl, phenyl-CVC3 alkylsulfonyl, camphorylsulfonyl, naphthylsulfonyl, trimethylphenylsulfonyl; or benzene A sulfonyl group which is substituted via one or more C2-C16 alkyl groups or (^-(alkoxy); and R'3 is a phenyldisulfonyl group, R4 is a phenyl group; Ci-C^ An alkyl group which is unsubstituted or substituted by (: 2 &lt; 12 alkoxycarbonyl; or a rule 4 is c2-c12 alkyl which is interrupted by one or more and which is derived from phenyl Substituted; or 仏 is 匕^^alkylsulfonyl; heart and heart are heart-cardiyl; and the heart is phenyl or CVC12 alkyl; but the premise is that if R' is 4-methylphenyl or 4 - octylphenyl, then R"3 is not a methanesulfonyl group. 7 - A compound of the formula I, II or III as claimed in claim 1 or a formula lb, lib as in claim 6 Or a special form of a thermally stable isomer of an Illb compound It is prepared by the following: (1) An acid mixture is used to treat a mixture of isomers of a compound of the formula X or XI oxime obtained by a conventional method, 5 (Please read the back of the note first and then fill out this page) Paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1295281 A8 B8 C8 D8, patent application scope N/〇~ΗI! (X) Λ x X and .Ο R〆, C 1 VIII XX / R2 H (XI), wherein h ' R2 and X are as defined in the first paragraph of the patent application, (2) the prepared single isomerized oxime compound and the relative formula xv, XVI or XVII acid _ Acid halide reaction, R3ci (XV) Rm3C1 (XVI) Cl-R, 3-C1 (XVII), wherein h and 1?, 3 are as defined in claim 1 of the patent application, and Rn3 is As defined in claim 6 of the patent application. 8 - Photopolymerizable composition, including: (a) 100% by weight of a compound which hardens under the action of an acid, or its solubility increases under the action of an acid And (b) 0.1 to 30% by weight of at least one of the photosensitive acid supply agents as in claim 6 A compound of formula lb, lib or Illb. 9. A method for crosslinking a compound which will crosslink under the action of an acid, the method comprising adding a compound of formula lb, lib and/or Illb as in claim 6 Among the above compounds, light is used to illuminate the entire region using light having a wavelength ranging from 150 to 1500 nm to form an image. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) (please read the note on the back and write this page first) Order: · 1295281 B8 C8 D8 Patent application scope 1 如 If you apply for a patent The method of item 9, which is for preparing a surface coating, a squirt ink, a printing plate, a dental composition, a color filter, a photoresist, or an image recording substance, or an image for recording a holographic image - Record the substance. ----------------------丨装-..... (Please read the notes on the back and fill out this page) ·. This paper size is applicable to China. National Standard (CNS) A4 specification (210 X 297 mm)