AU2002221606A1

AU2002221606A1 - Oxime derivatives and the use thereof as latent acids

Info

Publication number: AU2002221606A1
Application number: AU2002221606A
Authority: AU
Inventors: Toshikage Asakura; Akira Matsumoto; Masaki Ohwa; Hitoshi Yamato
Original assignee: Ciba Spezialitaetenchemie Holding AG; Ciba SC Holding AG
Current assignee: BASF Schweiz AG
Priority date: 2000-09-25
Filing date: 2001-09-18
Publication date: 2002-04-02
Also published as: US7244544B2; US20040002007A1; EP1320785A2; WO2002025376A3; KR100785758B1; KR20040004381A; US6986981B2; WO2002025376A2; TWI272451B; JP2004510189A; BR0114136A; JP4620325B2; ATE458211T1; US20060068325A1; DE60141339D1; CA2421206A1; EP1320785B1

Abstract

New oxime sulfonate compounds of the formula I, II, III, IV, V, VI and VII R1 is for example C1-C18alkylsulfonyl, R2 is halogen or C1-C10haloalkyl; R3 is for example unsubstitude or substituted phenylenedisulfonyl, diphenylenedisulfonyl, or oxydiphenylenedisulfonyl; Ar1 is for example a direct bond, C1-C12alkylene; -O-C-bond or a -O-Si-bond which cleaves upon the action of an acid; A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11 and A12 are for example a direct bond, -O-, or -S-, or are C1-C12alkylene or phenylene unsubstituted or substituted; Y1 is C1-C12alkylene which is for example substituted by OR4, or SR7; Y2 is e.g. a trivalent radical of C1-C12alkylene; Y3 is e.g. a tetravalent radical of C1-C12alkylene; X is halogen; Ar'1 is for example C1-C12alkyl which is unsubstituted or substituted; Ar''1 is for example phenylene; provided that at least one of the radicals Ar'1, Ar''1, is substituted by 1 to 3 groups of example halogen; R15, R16, R17 and R18 e.g. hydrogen or phenyl; R19, R20, R21, R22 R23 are e.g. phenyl; are especially suitable for the preparation of photoresists.

Description

Oxime derivatives and the use thereof as latent acids

The invention relates to new oxime derivatives, chemically amplified photoresist compositions comprising said compounds and to the use of the compounds as latent acids, which can be activated by irradiation with actinic electromagnetic radiation and electron beams.

In US 4540598 surface-coating compositions comprising photosensitive oxime sulfonate compounds, e.g. 4-chloro-α-trifluoroacetophenonoxime benzenesulfonate and customary acid-curable resins are disclosed. In US 4736055 2,2,2-trifluoro-1-phenyl-ethanone oxime- O-(4-hydroxyphenylsulfonate) is described as a component for the preparation of polymers which can be used as resins in positive photoresists. In US 5627011 and US 5759740 the use of α-(4-toluene-sulfonyloxyimino)-4-methoxybenzyl cyanide and -(4-toluene-sulfonylox- yimino)-3-thienylmethyl cyanide as latent acid catalysts in chemically amplified positive and negative photoresists for wavelengths of 340-390 nm, especially those in the radiation region of the mercury i line (365 nm) is described. In GB 2306958 the use of oxime-sulfonates as latent acid donors in positive and negative photoresists for wavelengths between 180 and 600 nm, especially those in the radiation region beyond 390 nm is reported. In US 5714625 non aromatic oc-(alkylsulfonyloxyimino)-1 -cyclohexenylacetonitriles and α-(alkylsulfonyloxyim- ino)-1 -cyclopentenylacetonitriles are disclosed. In EP 241423 oxime sulfonate compounds are employed in about 25% concentration as photolatent acid generators in non-chemically amplified positive resists. In Chemical Abstracts No. 97:144503, 78:97752, Synthesis (1995), 553, some fluoroketoxime sulfonate compounds are described as experimental products for synthetic studies.

In the art exists a need for reactive non-ionic latent acid donors that are thermally and chemically stable and that, after being activated by light, UV-radiation, X-ray irradiation or electron beams can be used as catalysts for a variety of acid-catalysed reactions, such as poly- condensation reactions, acid-catalysed depolymerisation reactions, acid-catalysed electro- philic substitution reactions or the acid-catalysed removal of protecting groups. A particular need exists for latent acid catalysts with high stability and good solubility in the field of chemically amplified photoresists .

Surprisingly, it has now been found that specific oxime derivatives, as described below, are especially suitable as catalysts for the aforementioned acid catalyzed reactions. The optical absorption spectra of the specific compounds of the invention are tunable over a wide range of the electromagnetic spectrum and particularly suitable for applications in the deep UV range. Furthermore, chemically amplified photoresist compositions comprising oxime derivatives of the present invention are thermally stable, even at high bake temperatures during processing and provide high photospeed.

The invention accordingly relates to a chemically amplified photoresist composition comprising

(a) a compound which cures upon the action of an acid or a compound whose solubility is increased upon the action of an acid; and

(b) as photosensitive acid donor, at least one compound of the formula I, II, III, IV, V, VI or VII

wherein

Ri is C C₁₈alkylsulfonyl, Cι-C₁₀haloalkylsulfonyl, camphorylsulfonyl, phenyl-C^Caalkylsul- fonyl, C₃-C₁₂cycloalkylsulfonyl, phenylsulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl, wherein the groups cycloalkyl, phenyl, naphthyl, anthracyl and phe- nanthryl of the radicals C₃-Cι₂cycloalkylsulfonyl ,phenyl-C C₃alkylsulfonyl, phenylsul- fonyl, naphthylsulfonyl, anthracylsulfonyl and phenanthrylsulfonyl are unsubstituted or substituted by one or more halogen, CrC₄haloalkyl, CN, NO₂, Cι-C₁₆alkyl, phenyl, C_r C₄alkylthio, OR₄, (CO)OR₇, C_rC₄alkyl-(CO)O-. R₇OSO₂- and/or -NR₅R₆; or R₁ is C₂-

C₆haloalkanoyl, halobenzoyl, or a group R₁₀ ;

X_L X₂ and X₃ independently of each other are O or S; R₂ is halogen or CrC₁₀haloalkyl;

R₃ is phenylenedisulfonyl, naphthylenedisulfonyl, , di- phenylenedisulfonyl, or oxydiphenylenedisulfonyl, wherein these radicals are unsubstituted or substituted by C C₁₂alkyl; or R₃ is C₂-Cι₂alkylenedisulfonyl; A is a direct bond, unsubstituted C C₁₂alkylene, C_rC₁₂alkylene which is substituted by C₃- C₃₀cycloalkyl; or Ari is C₃-C₃ocycloalkylene, Cι-C₈haloalkylene, C₂-C₁₂alkenylene, C₄-C₈- cycloalkenylene, C₆-Cι₂bicycloalkenylene; or Aη is phenylene, which is unsubstituted or substituted by one or more C C₁₂alkyl, C_rC₄haloalkyl, phenyl-CrC₃-alkyl, halogen, phenyl, OR₄, NR₅R₆, SR₇₎ SOR₇, and/or SO₂R₇, optionally the substituents OR_4> SR₇ and NR₅R₆ form 5- or 6-membered rings, via the radicals R₄, R₅, R₆ and/or R₇, with further substituents on the phenylene ring or with one of the carbon atoms of the phenylene ring; or A is naphthylene, anthracylene or phenanthrylene ring, wherein the radicals naphthylene, anthracylene and phenanthrylene are unsubstituted or substituted by C C₆alkyl, phenyl, OR₄, NR₅R₆, SR₇, SOR₇, and/or SO₂R_7r optionally the substituents OR₄, SR₇ and NR₅R₆ form 5- or 6-membered rings, via the radicals R₄, R_5j R₆ and/or R₇ with further substituents on the naphthylene, anthracylene or phenanthrylene ring or with one of the carbon atoms of the naphthylene, anthracylene or phenanthrylene ring; or A is a heteroarylene ring which is unsubstituted or substituted by CrCgalkyl, phenyl, OR₄, NR_SR₆, SR₇, SOR₇₎ and/or SO₂R₇₎ optionally the substituents OR₄, SR₇ and NR ₅Re form 5- or 6-membered rings, via the radicals R₄, R₅, R₆ and/or R₇ with further substituents on the heteroarylene ring or with one of the carbon atoms of the heteroarylene ring; wherein all radicals An optionally additionally are substituted by a group having a -O-C-bond or a -O-Si-bond which cleaves upon the action of an acid; Aι, A_2l A₃, A₄, A₅, Ae, A₇, Aβ, A₉, A₁₀, An and A₁₂ independently of each other are a direct bond, -O-, -S-, -NR -, -CO-, -O(CO)-, -S(CO)-, -NR₄(CO)-, -SO-, -SO₂-, or -OSO₂-; or Ai, A₂, A₃, A₄, A₅, A₆, A₇, A₈, A₉, A₁₀, An and A₁₂ are C_rC₁₂alkylene or phenylene wherein these radicals are unsubstituted or substituted by one or more CrC₁₂alkyl, C C₄haloalkyl, halogen, OR and/or SR₇;

Y₁ is C C₁₂alkylene which is substituted by OR₄, SR₇, halogen and/or phenyl; or Y^ is C₂- C₁₂alkylene, which is interrupted by one or more -O-, -S-, -NR₄-, -O(CO)-, -S(CO)-, -NR₄(CO)-, -SO-, -SO₂- and/or -OSO₂-, and the radical C₂-C₁₂alkylene being substituted by OR , SR₇, halogen and/or phenyl;

Y₂ is a trivalent radical of CrC^alkylene, phenylene, naphthylene, or a heterocyclic ring wherein these radicals are unsubstituted or substituted by Cι-Cι₂alkyl, halogen, OR₄ and/or SR₇;

Y₃ is a tetravalent radical of C Cι₂alkylene, phenylene, naphthylene, or a heterocyclic ring wherein these radicals are unsubstituted or substituted by Cι-C₁₈alkyl, halogen, OR₄ and/or SR₇;

X is halogen;

R is hydrogen, CrC^alkyl which is unsubstituted or substituted by phenyl, OH, CrC₁₂. alkoxy, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthio- carbonyl, NR₅R₆, C C₁₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl and/or by C₂-C₆alkanoyl; or R₄ is C₂-Cι₈alkyl which is interrupted by one or more -O-, and which is unsubstituted or substituted by phenyl, OH, C Cι₂alkoxy, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR₅R₆, C_rC₁₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl and/or by C₂-C₆alkanoyl; or R₄ is phenyl which is unsubstituted or substituted by OH, Cι-C₁₈alkyl, halogen and/or CrC₁₂alkoxy; or R₄ is C₂-C₁₈alkanoyl which is unsubstituted or substituted by phenyl, OH, CrCι₂alkoxy, C₂- C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR₅R₆, C C ₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl, and/or by C₂-C₆alkanoyl; or R₄ is CrCujalkylsulfonyl which is unsubstituted or substituted by phenyl, OH, C_rC₁₂al- koxy, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR₅R₆, d-Cu.alkylsuIfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyI, and/or by C₂-C₆alk- anoyl; or R₄ is phenylsulfonyl which is unsubstituted or substituted by one or more halogen, C₁-C₄haloalkyl, CN, NO₂, C C₁₆alkyl, phenyl, C_rC alkylthio, C C₁₂alkoxy and/or phenoxy; or R is benzoyl, C Cιohaloaikylsulfonyl, camphorylsulfonyl, phenyl- CrC₃alkylsulfonyl, C₃-C₁₂cycloalkylsuIfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl;

R₅ and R₆ independently of each other are hydrogen or C C₁₈alkyl which is unsubstituted or substituted by OH, C C alkoxy, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, phenylamino, phenylaminocarbonyl, CrC ₂alkylsulfonyl, phenylsulfonyl, (4-methyl-phenyl)sulfonyl and/or Cι-C₆alkanoyl; or R₅ and R₆ are C₂- C₁₈alkyl which is interrupted by one or more -O-, and which is unsubstituted or substituted by OH, C C₄alkoxy, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, phenylamino, phenylaminocarbonyl, CrC^alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl and/or C_rC₆alkanoyl; or R₅ and R₆ are phenyl which is unsubstituted or substituted by OH, CrC₁₈alkyl, halogen and/or C_rCι₂alkoxy; or R₅ and R₆ are C₂-C₁₈alkanoyl, which is unsubstituted or substituted by phenyl, OH, C Cι₂. alkoxy, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, phenylamino, phenylaminocarbonyl, C_rC₁₂alkylsulfonyl, phenylsulfonyl, (4- methylphenyl)sulfonyl, and/or by C₂-C₆alkanoyl; or R₅ and R₆ are CrC₁₈alkylsulfonyl which is unsubstituted or substituted by phenyl, OH, C_rC₁₂alkoxy, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, phenylamino, phenylaminocarbonyl, CrC₁₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl, and/or by C₂- C₆alkanoyl; or R₅ and R₆ are phenylsulfonyl which is unsubstituted or substituted by one or more halogen, C C₄haloalkyl, CN, NO₂, C C₁₆alkyl, phenyl, C C alkylthio, C_r C₁₂alkoxy and/or phenoxy; or R₅ and R₆ are benzoyl, CrC₁₀haloalkylsulfonyl, camphorylsulfonyl, phenyl-C C₃alkylsulfonyl, C₃-Cι cycloalkylsulfonyI, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl; or R₅ and R₆, together with the nitrogen atom to which they are attached, form a 5-, 6- or 7-membered ring which may be interrupted by - O- or by -NR -;

R₇ is hydrogen, phenyl, C_rC₁₈alkyl which is unsubstituted or substituted by phenyl, OH, C C₁₂alkoxy, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR₅R₆, C_rC₁₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl, and/or by C₂- C₆alkanoyl; or R₇ is C₂-C₁₈alkyl which is interrupted by one or more -O- and which is unsubstituted or substituted by phenyl, OH, C_rC₁₂aIkoxy, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR₅R₆, C_rCι₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)suIfonyl, and/or by C₂-C₆alkanoyl; or R₇ is C₂- C₁₈alkanoyl which is unsubstituted or substituted by phenyl, OH, CrC₁₂alkoxy, C₂- C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR₅R₆, CrC₁₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl, and/or by C₂-C₆alkanoyl; or R₇ is C Cι₈alkylsulfonyl which is unsubstituted or substituted by phenyl, OH, C_r C₁₂alkoxy, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR₅R₆, CrC₁₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl, and/or by C₂-C₆alkanoyl; or R₇ is phenylsulfonyl which is unsubstituted or substituted by one or more halogen, Cι-C₄haloalkyl, CN, NO , C_rC₁₆alkyl, phenyl, CrC₄alkylthio, CrC₁₂alkoxy and/or phenoxy; or R₇ is benzoyl, C-|-C-|ohaloalkylsulfonyl, camphorylsulfonyl, phenyl- Cι-C3alkylsulfonyl, C₃-C₁₂cycloalkylsulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl;

R₈, Rg and R₁₀ independently of one another are Chalky! which is unsubstituted or substituted by halogen; or R₈, R₉ and R₁₀ are phenyl which is unsubstituted or substituted by C C₄alkyl or halogen; or R₉ and R₁₀ together are 1 ,2-phenylene or C₂-C₆alkylene which is unsubstituted or substituted by C C alkyl or halogen;

Ar'! is CrC₁₂alkyl which is unsubstituted or substituted by C₃-C₃₀cycloalkyl; or Ar^ is C₃- C₃₀cycloalkyl, CrC₈haloalkyI, C₂-C₁₂alkenyl, C₄-C₈cycloalkenyl, C₆-C₁₂bicycIoalkenyl, camphoryl; or Ar'₁ is phenyl, which is unsubstituted or substituted by one or more C_rCι₂- alkyl, C C₄haloalkyl. phenyl-C C₃-alkyl, halogen, phenyl, OR'₄, NR'₅R'₆, SR'₇, SOR'_7l and/or SO₂R' , optionally the substituents OR'₄₎ SR'₇ and NR'₅R'e form 5- or 6-membered rings, via the radicals R' , R'₅, R'₆ and/or R'₇₎ with further substituents on the phenyl ring or with one of the carbon atoms of the phenyl ring; or Ar'i is naphthyl, anthracyl or phe- nanthryl, wherein the radicals naphthyl, anthracyl and phenanthryl are unsubstituted or substituted by C_rC₆alkyl, phenyl, OR'₄, NR'₅R'_6l SR'₇, SOR'₇₎ and/or SO₂R'₇, optionally the substituents OR'₄₎ SR'₇ and NR'₅R'₆ form 5- or 6-membered rings, via the radicals R' , R'_5j R'₆ and /or R'₇ with further substituents on the naphthyl, anthracyl or phenanthryl ring or with one of the carbon atoms of the naphthyl, anthracyl or phenanthryl ring; or Ar'! is a heteroaryl radical which is unsubstituted or substituted by C_rC₆alkyl, phenyl, OR'₄ , NR'sR'e, SR'₇, SOR'₇, and/or SO₂R'₇, optionally the substituents OR'₄, SR'₇ and NR'gR'e form 5- or 6-membered rings, via the radicals R'₄₎ R'₅, R'₆ and/or R'₇ with further substituents on the heteroaryl ring or with one of the carbon atoms of the heteroaryl ring; and wherein the radicals C_rC₁₂alkyl, phenyl, naphthyl, anthracyl, phenanthryl or the het- eroaryl radical optionally are substituted by 1 to 3 of the groups groups -

— O— fl S— 0^'M⁺ , — C π— 0^"M⁺ , — + N ¹—⁵ R₁₆ L - , ^' — + ? s ²—⁰ ₂₁ L _and/or O Rir ^■

— i— R₂₃ ^_ ; and wherein all radicals Ar'_! optionally additionally are substituted by a group having a - O-C-bond or a -O-Si-bond which cleaves upon the action of an acid;

Ar"! is phenylene, naphthylene, \ _ / ^CHj \ / » diphenylene or oxydi- phenylene, wherein these radicals are unsubstituted or substituted by CrC₁₂alkyl; or

Ar"_! is Cι-C₁₂alkylene or ^~ D-D-D— _ — ; wherein all radicals

Ar"! optionally are substituted by 1 to 3 of the groups groups _> o fl ₊ ^Ris _ ₊ R₂₀

— O— S— 0^'M⁺ , — C— 0^"M⁺ , — N— R_1β L , — S— R₂₁ L and/or O ^' R₁₇

-^l— R₂₃ L^~ ; and wherein all radicals Ar' optionally additionally are substituted by a group having a -

O-C-bond or a -O-Si-bond which cleaves upon the action of an acid;

D is -O-, -S-, -NR , -CO-, -O(CO)-, -S(CO)-, -NR'₄(CO)-, -SO-, -SO₂-, or -OSO₂-;

D-i is Ci-C₁₂alkylene or C₂-C₁₂alkylene, which is interrupted by one or more -O-, -S-, -NR'₄-, -CO-, -O(CO)-, -S(CO)-, -NR'₄(CO)-, -SO-, -SO₂-, and/or -OSO₂; and wherein the radicals CrCι₂alkylene and C₂-C₁₂alkylene optionally are substituted by 1 to 3 of the groups

groups L - , — X S-— R₂₁ L -

and/or — I — R₂₃ L ; R' is hydrogen, C_rCι₈alkyl which is unsubstituted or substituted by phenyl, OH, C C₁₂alkoxy, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR'sR'e, C_!-C₁₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyI and/or by C₂-C₆alkanoyl; or R'₄ is C₂-C₁₈alkyl which is interrupted by one or more -O-, and which is unsubstituted or substituted by phenyl, OH, C_rCι₂alkoxy, C₂-Cι₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR'₅R'₆₎ CrC₁₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl and/or by C₂-C₆alkanoyl; or R'₄ is phenyl which is unsubstituted or substituted by OH, C_rC₁₈alkyl, halogen and/or CrC^alkoxy; or R'₄ is C₂-C₁₈alkanoyl which is unsubstituted or substituted by phenyl, OH, Ci-Cι₂alkoxy, C₂- C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR'₅R'₆, CrC^alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl, and/or by C₂-C₆alkanoyl; or R'₄ is Cι-C₁₈alkylsulfonyi which is unsubstituted or substituted by phenyl, OH, C_!-C₁₂. alkoxy, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR'sR'e, C_!-C₁₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl, and/or by C₂-C₆alkanoyl; or R'₄ is phenylsulfonyl which is unsubstituted or substituted by one or more halogen, C_!-C₄haloalkyl, CN, NO₂, C_!-C₁₆alkyl, phenyl, C_rC alkylthio, C_!-C₁₂alkoxy and/or phenoxy; or R'₄ is benzoyl, C_rCi₀haloalkylsulfonyl, camphorylsulfonyl, phenyl- C!-C₃alkylsulfonyl, C₃-C₁₂cycloalkylsulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl; and wherein the radicals C_rC₁₈alkyI, C₂-C_!8alkyl, phenyl, C₂-C₁₈alkanoyl, phenylsulfonyl, benzoyl, CrC^haloalkylsulfonyl, camphorsulfonyl, phenyl-C_r C₃alkylsulfonyl, C₃-C₁₂cycloalkylsulfonyl, naphthylsulfonyl, anthracylsulfonyl or phe-

nanthrylsulfonyl optionally are substituted by 1 to 3 of the groups groups ,

— 0— and/or

— '-R₂₃ ^_ ;

R's and R'₆ independently of each other are hydrogen or Cι-C₁₈alkyl which is unsubstituted or substituted by OH, C_rC₄alkoxy, C₂-Cι₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, phenylamino, phenylaminocarbonyl, C Cι₂alkyl- sulfonyl, phenylsulfonyl, (4-methyl-phenyl)sulfonyl and/or Cι-C₆alkanoyl; or R'₅ and R'₆ are C₂-C₁₈alkyl which is interrupted by one or more -O-, and which is unsubstituted or substituted by OH, Cι-C₄alkoxy, C₂-Cι₂aIkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, phenylamino, phenylaminocarbonyl, Ci-C ₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl and/or C_rC₆alkanoyl; or R'₅ and R'₆ are phenyl which is unsubstituted or substituted by OH, CrCι₈alkyl, halogen and/or CrCι₂alkoxy; or R'₅ and R'₆ are C₂-C₁₈alkanoyl, which is unsubstituted or substituted by phenyl, OH, C Cι₂alkoxy, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, phenylamino, phenylaminocarbonyl, Cι-C₁₂alkylsulfonyl, phenylsulfonyl, (4- methylphenyl)sulfonyl, and/or by C₂-C₆alkanoyl; or R'₅ and R'₆ are CrC₁₈alkylsulfonyl which is unsubstituted or substituted by phenyl, OH, CrCι₂alkoxy, C₂-Cι₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, phenylamino, phenylaminocarbonyl, Cι-Cι₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl, and/or by C₂- C₆alkanoyl; or R'₅ and R'₆ are phenylsulfonyl which is unsubstituted or substituted by one or more halogen, C C₄haloalkyl, CN, NO₂, Cι-C₁₆alkyl, phenyl, C C₄alkylthio, C C₁₂alkoxy and/or phenoxy; or R'₅ and R'₆ are benzoyl, Cι-C₁₀haloalkylsulfonyl, cam- phorylsulfonyl, phenyl-CrC₃alkylsulfonyl, C₃-C₁₂cycloalkylsulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl; or R'₅ and R'₆, together with the nitrogen atom to which they are attached, form a 5-, 6- or 7-membered ring which may be interrupted by - O- or by -NRV; and wherein the radicals Cι-C₁₈alkyl, C₂-Cι₈alkyl, phenyl, C₂- C₁₈alkanoyl, Cι-C₁₈alkylsulfonyI, phenylsulfonyl, benzoyl, CrC^haloalkylsulfonyl, cam- phorsulfonyl, phenyl-CrC₃alkylsulfonyl, C₃-Cι₂cycloalkylsulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl optionally are substituted by 1 to 3 of the groups

groups _ 8!J_O- ⁺ _■ — 0- flS-0^{" +} , — ff C— O M . , ISI— R_1β L - , — X S-— R₂₁ L -

I I o o 17

+ — and/or 1 — R₂₃ L ;

R'₇ is hydrogen, phenyl, d-C₁₈alkyl which is unsubstituted or substituted by phenyl, OH, C!-C₁₂alkoxy- C₂-Cι₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR'sR'e, C_rC₁₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl, and/or by C₂-C₆alkanoyl; or R'₇ is C₂-C₁₈alkyl which is interrupted by one or more -O- and which unsubstituted or substituted by phenyl, OH, d-C^alkoxy, C₂- C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR'₅R'₆, CrC^alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl, and/or by C₂-C₆alkanoyl; or R'₇ is C₂-Cι₈alkanoyl which is unsubstituted or , substituted by phenyl, OH, C_r Cι₂alkoxy, C₂-Cι₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR'₅R'e, CrCι₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl, and/or by C₂-C₆alkanoyl; or R'₇ is CrC₁₈alkylsulfonyl which is unsubstituted or substituted by phenyl, OH, CrCι₂alkoxy, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR'sR'e, C_rCι₂alkylsulfonyl, phenylsulfonyl, (4- methylphenyl)sulfonyI, and/or by C₂-C₆alkanoyl; or R'₇ is phenylsulfonyl which is unsubstituted or substituted by one or more halogen, C_rC haloalkyl. CN, NO₂, C_rC₁₆alkyl, phenyl, C C alkylthio, CrC₁₂alkoxy and/or phenoxy; or R'₇ is benzoyl, d-dohaloalkylsulfonyl, camphorylsulfonyl, phenyl-Cι-C₃alkylsulfonyl, C₃-

Cι₂cycloalkylsulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl; and wherein the radicals Cι-Cι₈alkyl, C₂-C₁₈alkyl, C₂-C₁₈alkanoyl, Cι-C₁₈alkylsulfonyl, phenylsulfonyl, benzoyl, Cι-Cι₀haloalkylsulfonyl, camphorsulfonyl, phenyl-d-C₃alkylsulfonyl, C₃-C₁₂cycloalkylsulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl op-

tionally are substituted by 1 to 3 of the groups groups _>

— fl C— 0^'M⁺ , L _t — S²—⁰ R₂₁ L and/or —I— R₂₃ L _; provided that at least one of the radicals Ar'_1; Ar"_1f D^ R'₄₎ R'₅₍ R'₆ or R'₇ is substituted by

1 to 3 groups of groups s— O M⁺ - — 0— ⁰ S— 0^"M⁺ , — fl C— 0^"M⁺ . , — ♦? N"— R₁₆ L _; o O R₁₇

^R20

— S— R₂₁ L^~ and/or — I— ₂₃ L^~ ;

M⁺ is R₁₈— , R₂₄— I— R₂₃ , Li⁺, Na⁺, K⁺, Cs⁺, 1/2Mg²⁺, 1/2Ca²⁺ or

1/2Ba²⁺;

L- is F, CI^", Br-, I^", o^" , B(Rι₉)4^",

CIO₄ ^", BF₄ ^", PF₆ ^", AsF₆ ^" or SbF₆ ^"; Ri₅, Ri₆, Ri₇ and R₁₈ independently of each other are hydrogen or phenyl which is unsubstituted or substituted by one or more Cι-Cι₂alkyl, halogen, -NO₂, -CN, phenyl, C_rC₄- alkoxy, hydroxy, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, C_rC₄alkylthio, phenylthio, C₂-Cι₂alkanoyl, C₂-C₁₂alkanoyloxy, benzoyl and/or benzoyloxy; or Rι₅, Rι₆, Rι₇ and Rι₈ are Cι-C₁₂ alkyl, C₂-C₁₂alkyl which is interrupted by one or more -O-, and wherein the radicals d-Cι₂ alkyl and C₂-C₁₂alkyl are unsubstituted or substituted by one or more halogen, hydroxy, -NO₂, -CN, phenyl, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, C_rC₄alkylthio, phenylthio, C₂-C₁₂alkanoyl, C₂-Cι₂alkanoyloxy, benzoyl and/or benzoyloxy; or Rι₅ and Rι₆, if appropriate together with d-C₂alkylene, -O-, -S-, or -CO-, form fused ring; or R₁₅ and R₁₆, if appropriate together with CrC₂alkylene, -O-, -S-, or - CO-, form a 5-, 6-, or 7-membered ring; R₁₉ is phenyl, which is unsubstituted or substituted by one or more d-Cι₂alkyl, halogen, -NO₂, -CN, phenyl, C_rC₄alkoxy, C₂-C₁₂alkoxycarbonyl. phenoxy, phenoxycarbonyl, d- C₄alkylthio, phenylthio, C₂-C₁₂alkanoyl, C₂-Ci₂alkanoyloxy, benzoyl, benzoyloxy; or R₁₉ is Cι-C₁₂alkyl, or C₂-Cι₂alkyl which is interrupted by one or more -O-, wherein the radicals Cι-C₁₂alkyl, and C₂-C₁₂alkyl are unsubstituted or substituted by one or more halogen, hydroxy, -NO₂, -CN, phenyl, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, d- C₄alkylthio, phenylthio, C₂-C₁₂alkanoyl, C₂-C₁₂alkanoyloxy, benzoyl and/or benzoyloxy; R₂₀, R₂ι and R₂₂ independently of each other are phenyl, which is unsubstituted or substituted by one or more CrCι₂ alkyl, halogen, -NO , -CN, phenyl, C C₄alkoxy, hydroxy, C₂- C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, CrC₄alkylthio, phenylthio, C₂- C₁₂alkanoyl, C₂-Cι₂alkanoyldxy, benzoyl and/or benzoyloxy; or R₂₀, R₂ι and R₂ independently of each other are C C₁₂ alkyl, C₂-C₁₂alkyl which is interrupted by one or more -O-, and wherein the radicals C₁-C₁₂ alkyl and C₂-Cι₂alkyl are unsubstituted or substituted by one or more halogen, hydroxy, -NO₂, -CN, phenyl, C₂-d₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, C C₄alkylthio, phenylthio, C₂-Cι₂alkanoyl, C₂- C₁₂alkanoyloxy, benzoyl and/or benzoyloxy; or R₂₀ and R₂ι, if appropriate together with d-C₂alkylene, -O-, -S-, or -CO-, form a fused ring; or R₂₀ and R₂ι, if appropriate together with C!-C₂alkylene, -O-, -S-, or -CO-, form a 5-, 6-, or 7-membered ring; and R₂₃ and R₂₄ independently of each other are phenyl, which is unsubstituted or substituted by one or more of halogen, -NO₂, -CN, phenyl, C_rC₄alkoxy, hydroxy, C₂-C₁₂- alkoxycarbonyl, phenoxy, phenoxycarbonyl, d-C₄alkylthio, phenylthio, C₂-C₁₂alkanoyl, C₂- C₁₂alkanoyloxy, benzoyl and/or benzoyloxy; or R₂₃ and R₂₄, if appropriate together with C C₂alkylene, -O-, -S-, or -CO-, form fused ring. The compounds of the formulae I, II, III, IV, V, VI and VII are characterized in that they contain at least two halogen atoms on one of the carbon atoms next to the oxime group. Preferably the compounds contain three halogen atoms on one of the carbon atoms next to the oxime group.

C₁-Cι₈alkyl is linear or branched and is, for example, C₁-C₈-, -Cβ- or d-C₄-alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, preferably C₁-C₄alkyl, such as methyl, isopropyl or butyl. d-C₈alkyl, -Cβalkyl and C C₄a!kyl are likewise linear or branched and are, for example, as defined above up to the appropriate number of carbon atoms. Of interest are, for example, C_rC₈-, especially Cι-C₆-, preferably Cι-C -alkyl, such as methyl or butyl. R is for example C₂-Cι₂-, C -Cι₂-, C₈-Cι₂-, C₄-C₈-alkyl.

C₂-C₁₂alkyl, which is interrupted once or several times by -O-, is interrupted, for example, from one to five times, for example from one to three times or once or twice, by non-successive -O-. Accordingly, resulting structural units are for example: -O(CH₂)₂OH, -O(CH₂)₂OCH₃, -O(CH₂CH₂O)₂CH₂CH₃, -CH₂-O-CH₃, -CH₂CH₂-O-CH₂CH₃, -[CH₂CH₂O]_y- CH₃, wherein y = 1-5, -(CH₂CH₂O)₅CH₂CH₃, -CH₂-CH(CH₃)-O-CH₂-CH₂CH₃ or -CH₂- CH(CH₃)-O-CH₂-CH₃.

C₃-C₃₀cycloalkyl is a mono- or polycyclic aliphatic ring, for example a mono-, bi- or tricyclic aliphatic ring, e.g. C₃-C₂₀-, C₃-C₁₈-, C₃-Cι₂-, C₃-C₁₀cycloalkyl. Examples of monocyclic rings are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or cycloheptyl, especially cyclopentyl and cyclohexyl. Examples of polycyclic rings are perhydroanthracyl, perhydrophenyathryl, perhy- dronaphthyl, perhydrofluorenyl, perhydrochrysenyl, perhydropicenyl, adamantyl, bicyclo- [1.1.1]pentyl, bicyclo[4.2.2]decyl, bicyclo[2.2.2]octyl, bicyclo[3.3.2]decyl, bicyclo[4.3.2]undec- yl, bicyclo[4.3.3]dodecyl, bicyclo[3.3.3]undecyl, bicyclo[4.3.1]decyl, bicyclo[4.2.1]nonyl, bicyc- lo[3.3.1]nonyl, bicyclo[3.2.1]octyl and the like. Also "spiro"-cycloalkyl compounds are covered by the definition C₃-C₃₀cycloalkyl in the present context, e.g. spiro[5.2]octyl, spiro[5.4]dec- yl, spiro[5.5]undecyl. More examples of polycyclic cycloalkyl groups, which are subject of the respective definition in the compounds of the present invention are listed in EP 878738, page 11 and 12, wherein to the formulae (1)-(46) a bond to achieve the "yl" has to be added. The person skilled in the art is aware of this fact.

In general, the cycloaliphatic rings may form repeating structural units.

C₂-Cι₂alkenyl radicals may be mono- or polyunsaturated, linear or branched and are for example C₂-C₈-, C₂-C₆- or C₂-C₄alkenyl. Examples are allyl, methallyl, vinyl, 1,1-dimethylallyl, 1-butenyl, 3-butenyl, 2-butenyl, 1,3-pentadienyl, 5-hexenyl or 7-octenyl, especially allyl or vinyl.

C₄-C₈cycloalkenyl, may have one or more double bonds and is for example C₄-C₆-cycloal- kenyl or C₆-C₈-cycloalkenyl. Examples are cyclobutenyl, cyclopentenyl, cyclohexenyl or cy- clooctenyl, especially cyclopentenyl and cyclohexenyl, preferably cyclohexenyl.

C₆-Cι₂bicycloalkenyl refers to a bicyclic alkenyl group, which may possess one or more double bonds and wherein the double bonds are either situated in the same ring, but may also be situated in both rings. If several double bonds are present in the bicyclus, the double bonds are conjugated or non-conjugated, preferably the double bonds are conjugated. Examples are bicyclo[4.2.4]dodec-3,7-dien-5-yl, bicyclo[4.2.4]dodec-3-en-5-yl, bicyclo[4.2.4] dodec-4-en-6-yl, bicyclo[4.2.3]-non-3-en-5-yl, bicyclo[4.2.3]-non-4-en-6-yl, bicyclo[4.2.3]- non-7-en-8-yl, bicyclo[4.2.3]-non-8-en-7-yl, wherein the examples are referring to the follow¬

ing numbering

Cι-C₁₂alkylene is linear or branched and is, for example, C C₈-, C C₆- or C_rC₄-alkylene. Examples are methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, oc- tylene, nonylene, decylene, undecylene and dodecylene. Preferred is Cι-C₈alkylene, especially C₁-C₆alkylene, preferably C-ι-C₄alkylene, such as methylene or butylene. C₂-C₁₂alkylenedisulfonyl accordingly is an alkylene radical as indicated above, which at both "yl"-moieties bears a sulfonyl group. Examples are -SO₂-(CH₂CH₂)_z-SO₂-, with z = 1-6, e.g. -SO₂-CH₂CH₂-SO₂-, or -SO₂-CH(CH₃)CH₂-SO₂-. Phenylenedisulfonyl, diphenylenedisulfonyl and oxydiphenylendisulfonyl also bear the sulfon-

yl groups at the "yl" moiety. Accordingly, resulting structures are e.g

Substituted phenyl carries from one to five, for example one, two or three, especially one or two, substituents on the phenyl ring. The substitution is preferably in the 4-, 3,4-, 3,5- or 3,4,5-position of the phenyl ring.

The radicals d-Cι₈alkyl in the group d-dsalkylsulfonyl are meant to be linear or branched and have the meanings described above.

The radicals C₃-C₃₀cycloalkyl in the group C₃-C₃₀cyloalkylsuifonyl have the meanings described above.

When the radicals naphthyl, phenanthryl, heteroaryl and anthracyl are substituted by one or more radicals, they are, for example, mono- to penta-substituted, for example mono-, di- or tri-substituted, especially mono- or di-substituted.

When Ar¹ _! is a phenyl radical substituted by OR'₄ , NR'sR'e and/or by SR'₇ and the substituents OR'₄ , NR'₅R'_β and SR'₇ form 5- or 6-membered rings, via the radicals R'₄ , R'₅, R'₆ or R'_7l with other substituents on the phenyl ring or with one of the carbon atoms of the phenyl

ring, for example the following structural units are obtained \ J ,

ln the present application, the term "heteroaryl" denotes unsubstituted and substituted radi¬

cals, for example 3-thienyl, 2-thienyl, wherein R'₅ and R'₆ are as defined above, thianthrenyl, isobenzofuranyl, xanthenyl, phenoxanthiinyl,

- Ij or ^r j , wherein Y is S, O or NR'₄ and R'₄ is as defined above. Examples

thereof are pyrazolyl, thiazolyl, oxazolyl, isothiazolyl or isoxazolyl. Also included are, for ex-

ample, furyl, pyrrolyl, 1 ,2,4-triazolyl, or 5-membered ring heterocycles having a fused-on aromatic group, for example benzimidazolyl, benzothienyl, benzofuranyl, benzoxa- zolyl and benzothiazolyl.

Other examples of "heteroaryls" are pyridyl, especially 3-pyridyl, j| ^" ] , wherein R'₄ is

as defined above, pyrimidinyl, pyrazinyl, 1,3,5-triazinyl, 2,4-, 2,2- or 2,3-diazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, isoquinolyl, quinolyl, phenoxazinyl or phenazinyl. In this application, the term "heteroaryl" also denotes the radicals thioxanthyl, xanthyl,

' [R'_sR'_βNisrf - I I ' ^wnerein m is 0 or 1 and R'₄ , R'_5f R'₆ are as de-

fined above, or anthraquinonyl. Each of the heteroaryls may carry the sub- stituents indicated above or in claim 1.

Camphoryl, 10-camphoryI, are camphor-10-yl, namely

C₂-C₆alkanoyl is, for example, acetyl, propionyl, butanoyl or hexanoyl, especially acetyl.

CrC₄alkoxy is, for example, methoxy, ethoxy, propoxy and butoxy, it being possible for the alkyl radicals in alkoxy groups having more than two carbon atoms also to be branched. C C₄alkylhtio is for example, methylthio, ethylthio, propylthio and butylthio, it being possible for the alkyl radicals in alkylthio groups having more than two carbon atoms also to be branched.

C₂-C₆alkoxycarbonyl is (C_rC₅alkyl)-O-C(O)-, wherein C_rC₅alkyl is as defined above up to the appropriate number of carbon atoms. Examples are methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl or pentyloxycarbonyl, it being possible for the alkyl radicals in alkoxy groups having more than two carbon atoms also to be branched.

C₁-C₁₀haloalkyl and d-C₄haloalkyl are CrC₁₀- and C C₄-alkyl mono- or poly-substituted by halogen, Cι-Cι₀- and d-C₄-alkyl being, for example, as defined above. There are, for example, from one to three or one or two halogen substituents at the alkyl radical. Examples are chloromethyl, trichloromethyl, trifluoromethyl or 2-bromopropyl, especially trifluoromethyl or trichloromethyl. Preferred is d-Cι₀fluoroalkyl.

C₂-C₆haloalkanoyl is (C_!-C₅haloalkyl)-C(O)-, wherein d-C₅haloalkyl is as defined above up to the appropriate number of carbon atoms. Examples are chloroacetyl, trichloroacetyl, tri- fluoroacetyl, pentafluoropropionyl, perfluorooctanoyl, or 2-bromopropionyl, especially trifluo- roacetyl or trichloroacetyl.

Halobenzoyl is benzoyl which is mono- or poly-substituted by halogen and/or CrC₄haloalkyl, CrC₄-haloalkyl being as defined above. Examples are pentafluorobenzoyl, trichlorobenzoyl, trifluoromethylbenzoyl, especially pentafluorobenzoyl.

Halogen is fluorine, chlorine, bromine or iodine, especially chlorine or fluorine, preferably fluorine .

Phenyl-C C₃alkyl is, for example, benzyl, 2-phenylethyl, 3-phenylpropyl, -methylbenzyl or α,α-dimethylbenzyl, especially benzyl.

Oxydiphenylene is ^~° When R₅ and R₆ together with the nitrogen atom to which they are bonded form a 5-, 6- or 7- membered ring that may be interrupted by -O- or by -NR₄ -, for example the following struc-

tures are obtained o.o.Q - -

The definitions C_rCι₈alkylsulfonyl, phenyl-CrC₃alkylsulfonyl, camphorylsulfonyl, d-Ciohalo- alkylsulfonyl refer to the corresponding radicals d-Cι₈alkyl, phenyl-CrC₃alkyl, camphoryl and d-Ciohaloalkyl, as described in detail above, being linked to a suifonyl group (-SO₂-). Accordingly, also phenylsulfonyl, naphthylsulfonyl, anthracylsulfonyl and phenanthrylsulfonyl refer to the corresponding radicals linked to a suifonyl group. R_! is for example C₂-Cι₈-, C₄- C₁₂-, C₆-Cι₈-, C₄-Cιo-alkylsulfonyl.

Groups having a -O-C-bond or a -O-Si-bond which cleaves upon the action of an acid, and being substituents of the radical An, An' and Ar_!" are acid cleavable groups which increase the solubility of the compounds of formula I, II, III, IV, V, VI or VII in the alkaline developer after reaction with an acid. This effect is for example described in US 4883740. Examples of groups suitable as substitutents on the radical A , An' and An" are for example known orthoesters, trityl and benzyl groups, tert.-butyl esters of carboxylic acids, tert.-butyl carbonates of phenols or silyl ethers of phenols, e.g. -OSi(CH₃)₃, -CH₂-(CO)-O-C(CH₃)₃₍

-(CO)-O-C(CH₃)₃, -O-(CO)-O-C(CH₃)₃ or Rn and R_i2 inde- pendently of one another are hydrogen, CrC₆alkyl, C₃-C₈cycloalkyl, phenyl-C_rC₃alkyl, or Rn and R12 together are C₂-C₅alkylene, and

R₁₃ is unsubstituted or halogen-substitued Cι-C₁₀alkyl, unsubstituted or halogen-substitued

C₃-C₈cycloalkyl, or phenyl-C C₃-alkyl, or, if R^ and R₁₂ together are no C₂-C₅alkylene, R_i3 and Ri₂ together may be C₂-C₅alkylene, which may be interrupted by an -O-atom or an -S- atom.

C₃-C₃₀cycloalkylene is a biradical of mono- or polycyclic aliphatic ring, for example a mono-, bi- or tricyclic aliphatic ring, e.g. C₃-C₂₀-, C₃-C₁₈-, C₃-d₂-, C₃-Cιocycloalkylene. Examples of monocyclic rings are cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene or cyclo- heptylene, especially cyclohexylene. Examples of polycyclic rings are perhydroanthracylene, perhydrophenyathrylene, perhydronaphthylene, perhydrofluorenylene, perhydrochry- senylene, perhydropicenylene, adamantylene, bicyclo[1.1.1]pentylene, bicy- clo[4.2.2]decylene, bicy o[2.2.2]octylene, bicyclo[3.3.2]decylene, bicyclo[4.3.2]undecylene, bicyclo[4.3.3]dodecylene, bicyclo[3.3.3]undecylene, bicyclo[4.3.1]decylene, bicy- clo[4.2.1]nonylene, bicyclo[3.3.1]nonylene, bicydo[3.2.1]octylene and the like. Also "spiro"- cycloalkyl compounds are covered by the definition C₃-C₃₀cycloalkylene in the present context, e.g. spiro[5.2]octylene, spiro[5.4]decylene, spiro[5.5]undecylene. In general, the cycloaliphatic rings may form repeating structural units.

C C₈Haloalkylene is Cι-C₈-alkyIene mono- or poly-substituted by halogen, Cι-C₈-alkylene being, for example, as defined above. There are, for example, from one to three or one or two halogen substituents at the alkylene radical. Examples are chloromethylene, dichloro- methylene, difluoromethylene or 2-bromopropylene, especially difluoromethylene or di- chloromethylene.

C₂-Cι₂alkenylene radicals may be mono- or polyunsaturated, linear or branched and are for example C₂-C₈-, C₂-C₆- or C₂-C₄alkenylene. Examples are vinylene, propenylene, but-1 -en- ylene, but-2-enylene, penta-1 ,3-dienylene, especially vinylene.

C₄-C₈cycloalkenylene, may have one or more double bonds and is for example C -C₆-cyclo- alkenylene or C₈-C₈-cycloalkenylene. Examples are cyclobutenylene, cyclopentenylene, cyclohexenylene or cyclooctenylene, especially cyclopentenylene and cyclohexenylene, preferably cyclohexenylene.

C₆-C₁₂bicycIoalkenylene refers to a bicyclic alkenylene group, which may possess one or more double bonds and wherein the double bonds are either situated in the same ring, but may also be situated in both rings. If several double bonds are present in the bicyclus, the double bonds are conjugated or non-conjugated, preferably the double bonds are conjugated. Examples are bicyclo[4.2.4]dodec-3,7-dien-5-ylene, bicyclo[4.2.4]dodec-3-en-5- ylene, bicyclo[4.2.4]dodec-4-en-6-ylene, bicyclo[4.2.3]-non-3-en-5-ylene, bicyclo[4.2.3]-non- 4-en-6-ylene, bicyclo[4.2.3]-non-7-en-8-ylene, bicydo[4.2.3]-non-8-en-7-ylene, wherein the

examples are referring to the following numbering or Anthracylene is, for

Phenanthrylene. is, for example,

A trivalent radical of C C₁₂alkylene is linear or branched and is, for example, d-C₈-, d-C₆-

or C C₄-alkylene. Examples are — c CH. — c— c— C

H- — C— H ² H₂ H H₂

CH,

trivalent radical of naphthylene is or J T J • A trivalent radical of a het-

erocyclic ring is, for example,

and the like. A tetravalent radical of C C₁₂alkylene is linear or branched and

is, for example, C C₈-, C-|-C₆- or Cι-C₄-alkylene. Examples are are — c — , — c H— c π-

H . H, H H H, . H, H7H H7_H • A tetravalent radical of phenylene

IS A tetravalent radical of naphthylene is, for example, or

a heterocyclic ring is, for example,

and the like. The terms "and/or" or "or/and" in the claims are meant to express that not only one of the defined alternatives (substituents) may be present, but also several of the defined alternatives (substituents) together, namely mixtures of different alternatives (substituents).

The term "at least" is meant to define one or more than one, for example one or two or three, preferably one or two.

The invention also pertains to novel compounds of the formula I, II, III, IV, V, VI or VII.

Oxime derivatives (of formulae I, II, III, IV, V, VI and VII) can generally be prepared by methods described in the literature, for example by reacting suitable free oximes {R^ and R₃ = H) of formula I', II', III' IV, V or VI' with the desired (for example, sulfonic) acid halides or acid anhydrides of formula XV, XVI or XVII (for example, RiCI, R.-O-R_! or CI-R₃-CI).

Ri, R₂, R₃, X, An, An', An", Ai, A₂, A_3l A₄, A_5J A₆, A₇, A₈, A₉, AI₀, A_{11 t} A₁₂, Y_h Y₂ and Y₃ are defined as described above.

These reactions usually are carried out in an inert solvent such as for example toluene, methylene chloride, tetrahydrofuran (THF) or dimethylformamide (DMF) in the presence of a base, for example pyridine, a tertiary amine, such as triethylamine, or by reaction of the salt of an oxime with the desired acid chloride. These methods are disclosed, for example, in EP 48615. The sodium salts of oximes can be obtained, for example, by reacting the oxime in question with a sodium alcoholate in dimethylformamide. Such reactions are well known to those skilled in the art, and are generally carried out at temperatures in the range of -15 to +50°C, preferably 0 to 20°C.

The oximes required as starting materials can be obtained by a variety of methods described in standard chemistry textbooks (for instance in J. March, Advanced Organic Chemistry, 4th Edition, Wiley Interscience, 1992), or in specialized monographs, for example, S.R. Sandier & W. Karo, Organic functional group preparations, Vol. 3, Academic Press. One of the most convenient methods is, for example, the reaction of ketones with hydroxyl- amine or its salt in polar solvents like ethanol or aqueous ethanol. In that case, a base such as sodium acetate is added to control the pH of the reaction mixture. It is well known that the rate of the reaction is pH-dependent, and the base can be added at the beginning or continuously during the reaction. Basic solvents such as pyridine can also be used as base and/or solvent or cosolvent. The reaction temperature is generally the refluxing temperature of the mixture, usually about 60-120°C.

Another convenient synthesis of oximes is the nitrosation of "active" methylene groups with nitrous acid or an alkyl nitrite. Both alkaline conditions, as described for example in Organic Syntheses coll. Vol. VI (J. Wiley & Sons, New York, 1988), pp 199 and 840, and acidic conditions, as described, for example, in Organic Synthesis coll. vol V, pp 32 and 373, coll. vol. Ill, pp 191 and 513, coll. vol.ll, pp. 202, 204 and 363, are suitable for the preparation of the oximes used as starting materials for the compounds according to the invention. Nitrous acid is usually generated from sodium nitrite. The alkyl nitrite can for example be methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, isoamyl nitrite.

The described syntheses can result in the formation of isomeric forms of the compounds of formula I, II, III, IV, V, VI and VII. The double bond of the oximino group can exist in both the syn (cis, Z) and the anti (trans, £) form or as mixtures of the two geometrical isomers. In the present invention, both the individual geometrical isomers and any mixtures of two geometrical isomers can be used. The invention accordingly also relates to mixtures of isomeric forms of the compounds of formula I, II, III, IV, V, VI and VII.

The compounds of formula I, II, III, IV, V, VI and VII of the individual geometrical isomers (Z and E forms) and any mixtures of two geometrical isomers can be used, however, it has been found that the compounds of formula I, II, III, IV, V, VI and VII of a specific conformation (tentatively assigned as Z-form) are more thermally stable than the compounds of other conformation (tentatively assigned as E-form). Therefore, preferred use of the compounds of the present invention are of formula I, II, III, IV, V, VI and VII of the single more thermally stable isomer (tentatively assigned as Z-form).

The syntheses of the oximes required as starting materials can result in the formation of a mixture of isomeric forms. Surprisingly, it has been found that the mixture of isomeric forms of the oximes required as starting materials is converted to a single isomeric form (tentatively assigned as Z-form) by treatment with acid. Using these oximes of the single isomer (Z- form) as the starting materials, the compounds of formula I, II, III, IV, V, VI and VII of the thermally more stable single isomer are obtained. Accordingly the present invention also relates to a process for the synthesis of the thermally more stable isomer of the compounds of formula I, II, III, IV, V, VI and VII by 1) conversion of the corresponding isomeric mixture of oximes to the oximes of the a single isomeric form by treatment with an acid, and 2) reaction of the oximes of the single isomeric form with the desired acid halides.

Subject of the invention therefore is a process for the specific preparation of the thermally stable isomer of the oxime ester compounds of formula I, II, III, IV, V, VI and VII according to claim 1 by

(1) treating the isomeric mixture of the corresponding free oxime compounds of formula I', II', III', IV, V or VI' , obtained by conventional methods,

wherein R_{1 (} R₂, R₃, X, An, An', An", A_{1 f} A₂, A₃, A₄, A₅, A₆₎ A₇, A₈, A₉₎ A₁₀, An, A₁₂,

Yi, Y₂ and Y₃ are as defined in claim 1 , with an acid; and

(2) reacting the thus prepared single isomeric free oxime compound with the corresponding acid halides or acid anhydrides of formula XV, XVI or XVII RiCI (XV), Ri-O-R_! (XVI), CI-R₃-CI (XVII). The conversion reactions of the isomeric mixture of oximes to the desired single isomer are usually carried out in an inert solvent such as methylene chloride, ethyl acetate, toluene, tetrahydrofuran or dimethylformamide in the presence of an acid such as hydrochloric acid, sul- furic acid, acetic acid, trifluoroacetic acid, or trifluoromethanesulfonic acid. Such reactions are usually carried out at temperature in the range of -15°C to +120°C, preferably 0°C to 80°C, more preferably 5°C to 40°C. The compounds are isolated by methods known to the person skilled in the art, e.g. distillation, recrystallisation, chromatographic methods. Examples for conventional methods to obtain the oxime compounds of formula I', II¹, III', IV, V or VI ' as startng materials are given above.

Interesting are compounds of the formula I, II, III, IV, V, VI and VII, wherein X and R₂ are both fluorine.

Interesting are further compounds of formula I, II, III, IV and V, wherein Ri is Cι-C₁₈aIkylsuIfonyl, Cι-Cιohaloalkylsulfonyl, camphorylsulfonyl, phenyl-C_rC₃alkylsul- fonyl, phenylsulfonyl or naphthylsulfonyl, wherein the groups phenyl and naphthyl of the radicals phenyl-C₁-C₃alkylsuIfonyl, phenylsulfonyl and naphthylsulfonyl are unsubstituted or substituted by one or more halogen, Cι-C₁₆alkyl, d-C₄alkoxy; R₂ is fluorine; An is phenylene;

Ai, A₂, A₃, A₄, A₅, A₆, A₇, A₈, A₉, A10, An and Aι₂ independently of each other are a direct bond, -O-, -S- or -O(CO)-; or Ai, A₂, A₃, A₄, A₅, A₆, A₇, A₈, A₉, Aι₀, An and Aι₂ are C_rCι₂aIkylene or phenylene; Yi is Cι-Cι₂alkylene which is substituted by OR₄; Y₂ is a trivalent radical of Cι-Cι₂alkylene, phenylene or heterocyclic ring ; Y₃ is a tetravalent radical of CrCi₂alkylene; X is fluorine;

R₄ is hydrogen, phenyl, C C₁₈alkyl, C₂-d₈alkanoyl, benzoyl, C_rC₁₈alkylsulfonyl, C_r Ciohaloalkylsulfonyl, camphorylsulfonyl, phenyl-C₁-C₃alkylsulfonyl, phenylsulfonyl or naphthylsulfonyl, wherein the groups phenyl and naphthyl of the radicals phenyl-C C₃alkylsulfonyl, phenylsulfonyl and naphthylsulfonyl are unsubstituted or substituted by one or more halogen, C C₁₆alkyl, d-C₄alkoxy. Interesting are further compounds and photoresist compositions comprising the compounds of formula I, II, IV and/or V, wherein

Ri is Cι-C₁₈alkylsulfonyl, d-Ciohaloalkylsulfonyl, naphthylsulfonyl or phenylsulfonyl which is unsubstituted or substituted by halogen, wherein ;

R₂ is halogen;

A is phenylene; i, A₂, A₃, A₄, A₅, A₆, A₇, A₈, A₉, A₁₀, An and Aι₂ independently of each other are a direct bond, -O-, O(CO) or C C₁₂alkylene;

Yi is C_!-Cι₂alkylene which is substituted by OR₄; or Y! is C₂-Cι₂alkylene, which is interrupted by -OSO₂-;

Y₂ is a trivalent radical of Cι-Cι₂alkylene or a trivalent heterocyclic ring;

X is halogen;

R₄ is hydrogen or C₂-C₁₈alkanoyl;

Ar^ is phenyl, which is unsubstituted or substituted by OR'₄;

R'₄ is Cι-Cι₈alkyl which is unsubstituted or substituted by ;

R.5, 16, R17 and R₁₈ are hydrogen or Cι-Cι₂alkyl.

Interesting are also compounds and photoresist compositions comprising the compounds of formula I, II and/or V, wherein

Ri is C_rC₁₈alkylsulfonyl, or naphthylsulfonyl;

R₂ is halogen;

An is phenylene;

Ai, A₂, A₃, A₄, A₅, A₆, A₇, A₈, A₉, A₁₀, A and A₁₂ independently of each other are -O- or Cι-Cι₂alkylene;

Y! is Cι-Cι₂alkylene which is substituted by OR₄; or Yi is C₂-C₁₂alkylene, which is interrupted by -OSO₂-; Y₂ is a trivalent heterocyclic ring;

X is halogen;

R₄ is hydrogen or C₂-C₁₈alkanoyl; Ar'i is phenyl, which is unsubstituted or substituted by OR'₄;

R'₄ is d-Cι₈alkyi which is unsubstituted or substituted by _>

R15, Rie, R 17 and Rι₈ are hydrogen or C Cι₂alkyl.

Of special interest are compounds of the formula V, VI or VII, wherein Ar'i is phenyl, which is unsubstituted or substituted by one or more of the radicals d -C_halky!, OR'₄ and/or SR'₇;

D is -O-or -S-;

D! is C Cι₂alkylene;

R'₄ is hydrogen, phenyl, - salkyl, C₂-Cι₈alkanoyl, benzoyl;

R'₇ is hydrogen, phenyl, Cι-C₁₈alkyl, C₂-Cι₈alkanoyl, benzoyl; provided that at least one of the radicals Ar¹ _!, Ar'¹ _!, D, D_{1 t} R'₄ or R'₇ is substituted by 1 to 3

groups of — ? s\— O^'M⁺ , — O— S π— 0^"M⁺ , — C ιι— O M . — + Nι— R₁₆ L _; O o R₁₇

M⁺ is R₂₂ or R₂— I— R₂₃ ; L^" is CI^", Bf or l^";

Ri5, Rie, Rι and R₁₈ independently of each other are hydrogen or phenyl, or Rι₅, R₁₆, Rι₇ and R₁₈ independently of each other are C_rC₁₂ alkyl which is unsubstituted or substituted by one or more of the radicals hydroxy and/or phenyl;

R₂₀, R₂ι and R₂₂ independently of each other are phenyl, which is unsubstituted or substituted by one or more of the radicals d-Cι₂ alkyl and/or d-C₄alkoxy; or R₂₀, R₂ι and R₂₂ independently of each other are C_rC₁₂ alkyl;

R₂₃ and R₂₄ independently of each other are phenyl, which is unsubstituted or substituted by one or more of the radicals Cι-C₁₂alkyl and/or C_rC₄aIkoxy. Especially preferred are

Evidently, the methylsulfonyl or methylcarbonyl groups can also be replaced by other longer chain alkylsulfonyl or alkylcarbonyl groups. Also the methyl or propyl groups of the oxime-O- alkylsulfonate groups may easily be replaced by other alkyl or aryl groups. These compounds are also subject of the present invention.

The compounds of formulae I, II, III, IV, V, VI or VII can be used as photosensitive acid donors in a photoresist. Resist systems can be prepared by image-wise irradiation of systems comprising compounds of formulae I, II, III, IV, V, VI or VII, followed by a developing step.

A chemically amplified photoresist is understood to be a resist composition wherein the radiation sensitive component provides a catalytic amount of acid which subsequently catalyses a chemical reaction of at least one acid-sensitive component of the resist. Resulting is the induction of a solubility difference between the irradiated and non-irradiated areas of the resist. Because of the catalytic nature of this process one acid molecule can trigger reactions at multiple sites as it diffuses through the reactive polymer matrix, from one reaction site to the next, as long as it is not trapped or destroyed by any secondary reaction. Therefore, a small acid concentration is sufficient to induce a high difference in the solubility between exposed and unexposed areas in the resist. Thus, only a small concentration of the latent acid compound is necessary. As a result, resists with high contrast and high transparency at the exposure wavelength in optical imaging can be formulated, which in turn produce steep, vertical image profiles at high photosensitivity. However, as a result of this catalytic process, it is required that the latent acid catalysts are chemically and thermally very stable (as long as not irradiated) in order not to generate acid during resist storage or during processing, which - in most cases - requires a post exposure bake step to start or to complete the catalytic reaction which leads to the solubility differential. It is also required to have good solubility of the latent catalysts in the liquid resist formulation and the solid resist film to avoid any particle generation which would interfere with the application of these resists in microelectronic manufacturing processes.

In contrast, positive resist materials which are not based on the chemical amplification mechanism must contain a high concentration of the latent acid, because it is only the acid concentration which is generated from the latent acid under exposure which contributes to the increased solubility of the exposed areas in alkaline developer. Because small acid concentration has only a little effect on the change of the dissolution rate of such resist and the reaction proceeds typically without a post exposure bake here, the requirements regarding chemical and thermal stability of the latent acid are less demanding than for chemically am- plified positive resists. These resists require also a much higher exposure dose to generate enough acid for achieving sufficient solubility in the alkaline developer in the exposed areas and also suffer from the relatively low optical transparency (due to the high concentration of latent acid necessary) and thus also lower resolution and sloped images. Resist compositions based on non-chemically amplified technology are therefore inferior in photosensitivity, resolution and image quality compared to chemically amplified resists.

From the above it becomes clear that chemical and thermal stability of a latent catalyst is vital for a chemically amplified resist and that latent acids which can work in a non-chemically amplified resist are not necessarily applicable to chemically amplified resists because of the different acid diffusion requirements, acid strength requirements and thermal and chemical stability requirements.

Preference is given to photoresist compositions, wherein the compounds of formula 1, 11, 111, IV, V, VI and VII wherein X and R₂ are both fluorine.

Preferred chemically amplified photoresist compositions of the present invention are those comprising compounds of the formula I, II, III and IV, wherein

Ri is d-dsalkylsulfonyl, d-Ciohaloalkylsulfonyl, camphorylsulfonyl, phenyl-d-C₃alkylsul- fonyl, phenylsulfonyl or naphthylsulfonyl, wherein the groups phenyl and naphthyl of the radicals phenyl-d-C₃alkylsulfonyl, phenylsulfonyl and naphthylsulfonyl are unsubstituted or substituted by one or more halogen, d-Cι₆alkyl or C C₄alkoxy;

R₂ is fluorine;

A is phenylene;

Ai, A₂, A₃, A₄, A₅, A₆, A₇, A₈, A₉, Aι₀, An and Aι₂ independently of each other are a direct bond, -O-, -S- or -O(CO)-; or A_1t A₂, A₃, A , A₅, A₆, A₇, A₈, A₉, A₁₀, An and A₁₂ are d- Cι₂alkylene or phenylene;

Yi is Cι-Cι₂alkylene which is substituted by OR₄;

Y₂ is a trivalent radical of C_rCι₂alkylene, phenylene or heterocyclic ring ;

Y₃ is a tetravalent radical of C_rC₁₂alkylene;

X is fluorine;

R₄ is hydrogen, phenyl, C_rC₁₈alkyl, C₂-Cι₈alkanoyl, benzoyl, d-Cisalkylsulfonyl, C C₁₀- haloalkylsulfonyl, camphorylsulfonyl, phenyl-C_rC₃alkylsulfonyl, phenylsulfonyl or naphthylsulfonyl, wherein the groups phenyl and naphthyl of the radicals phenyl-C_rC₃alkylsulfonyl, phenylsulfonyl and naphthylsulfonyl are unsubstituted or substituted by one or more halogen, C Cι₆alkyl or C C₄alkoxy.

Of special interest are chemically amplified photoresist compositions comprising compounds of the formula V, VI or VII, wherein

Ar'i is phenyl, which is unsubstituted or substituted by one or more of the radicals d-C₁₂- alkyl, OR'₄ and/or SR'₇;

D is -O-or -S-;

Di is C_rCι₂alkylene;

R' is hydrogen, phenyl, Cι-Cι₈alkyl, C₂-Cι₈alkanoyl, benzoyl;

R'₇ is hydrogen, phenyl, Cι-C₁₈alkyl, C₂-Cι₈alkanoyl, benzoyl; provided that at least one of the radicals Ar'i, Ar"ι, D, D_{1 (} R'₄ or R'₇ is substituted by 1 to 3

groups of —

M⁺ is R₁₈— N ιl-⁵R₁₆ , R₂₀ _ Sf R₂₂ . R₂— I R_{24 ;}

^R17

L^" is CI^", Br or l^";

Ri5, Rie, R17 and R₁₈ independently of each other are hydrogen or phenyl, or Rι₅, Rι₆, Ri_? and R₁₈ independently of each other are d-Cι₂ alkyl which is unsubstituted or substituted by one or more of the radicals hydroxy and/or phenyl;

R₂₀, R₂ι and R₂₂ independently of each other are phenyl, which is unsubstituted or substituted by one or more of the radicals C_rCι₂ alkyl and/or C_rC₄alkoxy; or R₂₀, R₂₁ and R₂₂ independently of each other are C Cι₂alkyl;

R₂₃ and R₂₄ independently of each other are phenyl, which is unsubstituted or substituted by one or more of the radicals d-Cι₂ alkyl and/or d-C₄alkoxy.

In other preferred compositions according to the invention the radicals Ar₁₍ Ar^ and An" are substituted by a group having a -O-C-bond or a -O-Si-bond which cleaves upon the action of an acid. The difference in resist solubility, between irradiated and non-irradiated sections that occurs as a result of the acid-catalysed reaction of the resist material during or after irradiation of the resist may be of two types depending upon which further constituents are present in the resist. If the compositions according to the invention comprise components that increase the solubility of the composition in the developer after irradiation, the resist is positive. The invention accordingly relates to a chemically amplified positive photoresist.

If, on the other hand, the components of the formulation reduce the solubility of the composition after irradiation, the resist is negative. The invention accordingly relates also to a chemically amplified negative photoresist.

A monomeric or polymeric compound which - in the unexposed areas - reduces the dissolution rate of an additionally present alkaline soluble binder resin in the resist formulation and which is essentially alkali-insoluble in the unexposed areas so that the resist film remains in the unexposed area after development in alkaline solution, but which is cleaved in the presence of acid, or is capable of being rearranged, in such a manner that its reaction product becomes soluble in the alkaline developer is referred to hereinafter as dissolution inhibitor.

T i The invention includes, as a special embodiment a chemically amplified positive alkaline- developable photoresist composition, comprising

(a1) at least one polymer having acid-labile groups which decompose in the presence of an acid and increase the solubility of the resist film in an aqueous alkaline developer solution in the exposed area and (b) at least one compound of formula I, II, III, IV, V, VI or VII.

A further embodiment of the invention is a chemically amplified positive alkaline-developable photoresist composition, comprising

(a2) at least one monomeric or oligomeric dissolution inhibitor having at least one acid-labile group which decomposes in the presence of acid and increases the solubility in an aqueous alkaline developer solution and at least one alkali-soluble polymer and,

(b) at least one compound of formula I, II, III, IV, V, VI or VII. Another specific embodiment of the invention resides in a chemically amplified positive alkaline-developable photoresist composition, comprising

(a1) at least one polymer having acid labile groups which decompose in the presence of an acid and increase the solubility in an alkaline developer in the exposed area; (a2) a monomeric or oligomeric dissolution inhibitor, having at least one acid labile group, which decomposes in the presence of an acid and increase the alkaline solubility in the exposed area;

(a3) an alkali-soluble monomeric, oligomeric or polymeric compound at a concentration which still keeps the resist film in the unexposed area essentially insoluble in the alkaline developer, and (b) at least one compound of formula I, II, III, IV, V, VI or VII.

The invention therefore pertains to a chemically amplified photoresist composition, comprising

(a1) at least one polymer having an acid-labile group which decomposes in the presence of an acid to increase the solubility in aqueous alkaline developer solution and/or (a2) at least one monomeric or oligomeric dissolution inhibtor having an acid-labile group which decomposes in the presence of an acid to increase the solubility in aqueous alkaline developer solution and/or

(a3) at least one alkali-soluble monomeric, oligomeric or polymeric compound; and (b) as photosensitive acid donor, at least one compound of formula I, II, III, IV, V, VI or VII.

The compositions may comprise additionally to the component (b) other photosensitive acid donors and/or (c) other additives.

Such chemically amplified positive resist systems are described, for example, in E. Reich- manis, F. M. Houlihan, O. Nalamasu, T. X. Neenan, Chem. Mater. 1991 , 3, 394; or in C. G. Willson, "Introduction to Microlithography, 2nd. Ed.; L S. Thompson, C. G. Willson, M. J. Bowden, Eds., Amer. Chem. Soc, Washington DC, 1994, p. 139.

Suitable examples of acid-labile groups which decompose in the presence of an acid to produce aromatic hydroxy groups, carboxylic groups, keto groups and aldehyde groups and increase the solubility in aqueous alkaline developer solution are, for example, alkoxyalkyl ether groups, tetrahydrofuranyl ether groups, tetrahydropyranyl ether groups, tert.-alkyl ester groups, trityl ether groups, silyl ether groups, alkyl carbonate groups as for example tert.-bu- tyloxycarbonyloxy-, trityl ester groups, silyl ester groups, alkoxymethyl ester groups, cumyl ester groups, acetal groups, ketal groups, tetrahydropyranyl ester groups, tetrafuranyl ester groups, tertiary alkyl ether groups, tertiary alkyl ester groups, and the like.

The polymer having functional groups capable of decomposing by the action of an acid to enhance solubility of the resist film comprising this polymer in an alkaline developing solution, which can be incorporated in the positive resist according to the present invention, may have the acid-labile groups in the backbone and/or side chains thereof, preferably in side chains thereof.

The polymer having acid-labile groups suitable for the use in the present invention can be obtained with a polymer analogous reaction where the alkaline soluble groups are partially or completely converted into the respective acid labile groups or directly by (co)-polymerization of monomers which have the acid labile groups already attached, as is for instance disclosed in EP 254853, EP 878738, EP 877293, JP-A-2-25850, JP-A-3-223860, and JP-A-4-251259.

The polymers which have acid labile groups pendant to the polymer backbone, in the present invention preferably are polymers which have, for example silylether, acetal, ketal and alkoxyalkylester groups (called "low-activation energy blocking groups") which cleave completely at relatively low post exposure bake temperatures (typically between room temperature and 110°C) and polymers which have, for example, tert-butylester groups or tert.- butyloxycarbonyl (TBOC) groups or other ester groups which contain a secondary or tertiary carbon atom next to the oxygen atom of the ester bond (called "high-activation energy blocking groups") which need higher bake temperatures (typically > 110°C) in order to complete the deblocking reaction in the presence of acid. Hybrid systems can also be applied, wherein, both, high activation energy blocking groups as well as low activation energy blocking groups are present within one polymer. Alternatively, polymer blends of polymers, each utilizing a different blocking group chemistry, can be used in the photosensitive positive resist compositions according to the invention.

Preferred polymers which have acid labile groups are polymers and co-polymers comprising the following distinct monomer types: 1 ) monomers that contain acid-labile groups which decompose in the presence of an acid to increase the solubility in aqueous alkaline developer solution and

2) monomers that are free of acid labile groups and free of groups that contribute to the alkaline solubility and/or

3) monomers that contribute to aqueous alkaline solubility of the polymer.

Examples of monomers of type 1) are: non-cyclic or cyclic secondary and tertiary-alkyl (meth)acrylates such as butyl acrylate, including t-butyl acrylate, butyl methacrylate, including t-butyl methacrylate, 3-oxocyclohexyl (me- th)acrylate, tetrahydropyranyl (meth)acrylate, 2-methyl-adamantyl (meth)acrylate, cyclohexyl (meth)acrylate, norbomyl (meth)acrylate, (2-tetrahydropyranyl)oxynorbonylaIcohol acrylates, (2-tetrahydropyranyI)oxymethyltricyclododecanemethanol methacrylates, trimethylsilylmethyl (meth)acryiate, (2-tetrahydropyranyl)oxynorbonylalcohol acrylates, (2-tetrahydropyranyl)oxy- methyltricyclododecanemethanol methacrylates, trimethylsilylmethyl (meth)acrylate o-/m-/p- (3-oxocyclohexyloxy)styrene, o-/m-/p- (1-methyl-1-phenylethoxy)styrene, o-/m-/p- tetrahydro- pyranyloxystyrene, o-/m-/p- adamantyloxystyrene, o-/m-/p- cyclohexyloxystyrene, o-/m-/p- norbornyloxystyrene, non-cyclic or cyclic alkoxycarbonylstyrenes such as o-/m-/p- butoxycar- bonylstyrene, including p- t-butoxycarbonylstyrene, o-/m-/p- (3-oxocyclohexyloxycarbonyl)- styrene, o-/m-/p- (1-methyl-1-phenylethoxycarbonyl)styrene, o-/m-/p- tetrahydropyranyloxy- carbonylstyrene, o-/m-/p- adamantyloxycarbonylstyrene, o-/m-/p- cyclohexyloxycarbonylsty- rene, o-/m-/p- norbornyloxycarbonylstyrene, non-cyclic or cyclic alkoxycarbonyloxystyrenes such as o-/m-/p- butoxycarbonyloxystyrene, including p- t-butoxycarbonyloxystyrene, , o-/m- /p- (3-oxocyclohexyloxycarbonyloxy)styrene, o-/m-/p- (1-methyl-1-phenylethoxycarbonyloxy)- styrene, o-/m-/p- tetrahydropyranyloxycarbonyloxystyrene, o-/m-/p- adamantyloxycarbonylox- ystyrene, o-/m-/p- cyclohexyloxycarbonyloxystyrene, o-/m-/p- norbornyloxycarbonyloxystyre- ne, non-cyclic or cyclic alkoxycarbonylalkoxystyrenes such aso/m/p-butoxycarbonylmethoxy- styrene, p- t-butoxycarbonylmethoxystyrene, o-/m-/p- (3-oxocyclohexyloxycarbonylmethoxy)- styrene, o-/m-/p- (1-methyl-1-phenylethoxycarbonylmethoxy)styrene, o-/m-/p- tetrahydropy- ranyloxycarbonylmethoxystyrene, o-/m-/p- adamantyloxycarbonylmethoxystyrene, o-/m-/p- cyclohexyloxycarbonylmethoxystyrene, o-/m-/p- norbornyloxycarbonylmethoxystyrene, trime- thylsiloxystyrene, dimethyl(butyl)siloxystyrene, unsaturated alkyl acetates such as isopropen- yl acetate and the derivatives of thereof. Monomers of type 1) bearing low activation energy acid labile groups include, for example, p- or m-(1 -methoxy-1 -methylethoxy)-styrene, p- or m-(1-methoxy-1-methylethoxy)- methyl- styrene , p-or m-(1 -methoxy-1 -methylpropoxy)styrene, p-or m-(1 -methoxy-1 -methylpropoxy) methylstyrene , p- or m-(1-methoxyethoxy)-styrene , p- or m-(l-methoxyethoxy)- methylstyre- ne, p- or m-(1-ethoxy-1-methylethoxy)styrene , p- or m-(1 -ethoxy-1 -methylethoxy)- methylstyrene, p- or m-(1 -ethoxy-1 -methylpropoxy)styrene, p- or m-(1 -ethoxy-1 -methylpropoxy) - methylstyrene , p- or m-(1 -ethoxyethoxy)styrene, p- or m-(1 -ethoxyethoxy)- methylstyrene, p- (1 -ethoxyphenyl-ethoxy)styrene, p- or m-(1-n-propoxy-1-metyIethoxy)styrene, p- or m-(1-n- propoxy-1 -metylethoxy) - methylstyrene, p- or m-(1-n-propoxyethoxy)styrene, p- or m-(1-n- propoxyethoxy)-methylstyrene, p- or m-(1 -isopropoxy-1 -methylethoxy)styrene, p- or m-(1 -isopropoxy-1 -methylethoxy)-methylstyrene, p- or m-(1-isopropoxyethoxy)styrene , p- or m-(1- isopropoxyethoxy)-methylstyrene, p- or m-(1 -isopropoxy-1 -methylpropoxy)styrene, p- or m- (1 -isopropoxy-1 -methylporpoxy)-methylstyrene, p- or m-(1-isopropoxypropoxy)styrene, p- or m-(1-isopropoxyporpoxy)-methylstyrene, p- or m-(1-n-butoxy-1-methylethoxy)styrene, p- or m-(1 -n-butoxyethoxy)styrene , p- or m-(1-isobutoxy-1-methylethoxy)styrene, p- or m-(1-tert- butoxy-1-methylethoxy)styrene, p- or m-(1 -n-pentoxy-1 -methylethoxy)styrene, p- or m-(1-iso- amyloxy-1-methylethoxy)styrene , p- or m-(1-n-hexyloxy-1-methylethoxy)styrene, p- or m-(1- cyclohexyloxy-1-methylethoxy)styrene, p- or m-(1 -trimethylsilyloxy-1 -methylethoxy)styrene, p- or m-(1 -trimethylsilyloxy-1 -methylethoxy)-methylstyrene, p- or m-(1-benzyloxy-1-methyl- ethoxy)styrene, p- or m-(1-benzyloxy-1-methylethoxy)-methylstyrene, p- or m-(1 -methoxy-1 - methylethoxy)styrene, p- or m-(1 -methoxy-1 -methylethoxy)-methylstyrene, p- or m-(1 -trimethylsilyloxy-1 -methy!ethoxy)styrene p- or m-(1 -trimethylsilyloxy-1 -methylethoxy)-methylstyre- ne. Other examples of polymers having alkoxyalkylester acid labile groups are given in US 5225316 and EP 829766. Examples of polymers with acetai blocking groups are given in US 5670299, EP 780732, US 5627006, US 5558976, US 5558971 , US 5468589, EP 704762, EP 762206, EP 342498, EP 553737 and described in ACS Symp. Ser. 614, Microelectronics Technology, pp. 35-55 (1995) and J. Photopolymer Sci. Technol. Vol. 10, No. 4 (1997), pp. 571-578. The polymer used in the present invention is not limited thereto.

With respect to polymers having acetal groups as acid-labile groups, it is possible to incorporate acid labile crosslinks as for example described in H.-T. Schacht, P. Falcigno, N. Muen- zel, R. Schulz, and A. Medina, ACS Symp. Ser. 706 (Micro- and Nanopatteming Polymers), p. 78-94, 1997; H.-T. Schacht, N. Muenzel, P. Falcigno, H. Holzwarth, and J. Schneider, J. Photopolymer Science and Technology, Vol.9, (1996), 573-586. This crosslinked system is preferred from the standpoint of heat resistance of the resist patterns.

Monomers with high activation energy acid labile groups are, for example, p-tert.-butoxycar- bonyloxystyrene, tert.-butyl-acrylate, tert.-butyl-methacrylate, 2-methyl-2-adamantyl-methac- rylate, isobomyl-methacrylate.

Examples of comonomers according to type 2) are: aromatic vinyl monomers, such as styrene, oc-methylstyrene, acetoxystyrene, α-methyinaph- thylene, acenaphthylene, vinyl alicyclic compounds such as vinyl norbomane, vinyl adaman- tane. vinyl cyclohexane, alkyl (meth)acrylates such as methyl methacrylate, acrylonitrile, vin- ylcyclohexane, vinylcyclohexanol, as well as maleic anhydride.

Examples of comonomers according to type 3) are: vinyl aromatic compounds such as hydroxystyrene, acrylic acid compounds such as methac- rylic acid, ethylcarbonyloxystyrene and derivatives of thereof. These polymers are described, for example, in US 5827634, US 5625020, US 5492793, US 5372912, EP 660187, US 5679495, EP 813113 and EP 831369. Further examples are crotonic acid, isocrotonic acid, 3-butenoic acid, acrylic acid, 4-pentenoic acid, propiolic acid, 2-butynoic acid, maleic acid, fumaric acid, and acetylenecarboxylic acid. The polymer used in the present invention is not limited thereto.

The content of acid labile monomers in the polymer may vary over a wide range and depends on the amount of the other comonomers and the alkaline solubility of the deprotected polymer. Typically, the content of monomers with acid labile groups in the polymer is between 5 and 60 mol%. If the content is too small, too low development rates and residues of the resist in the exposed areas result. If the content of acid labile monomers is too high, resist patterns are poorly defined (eroded) after development and narrow features cannot be resolved anymore and/or the resist looses its adhesion to the substrate during development. Preferably the copolymers which have acid labile groups have a M_w of from about 3'000 to about 200O00, more preferably from about 5'000 to about 50O00 with a molecular weight distribution of about 3 or less, more preferably a molecular weight distribution of about 2 or less. Non-phenolic polymers, e.g. a copolymer of an alkyl acrylate such as t-butyl acrylate or t-butyl-methacrylate and a vinyl alicyclic compound, such as a vinyl norbonanyl or vinyl cyclo- hexanol compound, also may be prepared by such free radical polymerization or other known procedures and suitably will have a Mw of from about 8'000 to about 50O00, and a molecular weight distribution of about 3 or less.

Other comonomers may suitably be added in an appropriate amount for the purpose of controlling the glass transition point of the polymer and the like.

In the present invention a mixture of two or more polymers having acid-labile groups may be used. For example, use may be made of a mixture of a polymer having acid-labile groups, which are cleaved very easily, such as acetal groups or tetrahydropyranyloxy- groups and a polymer having acid-cleavable groups, that are less easily cleaved, such as for example tertiary alkyl ester groups. Also, acid cleavable groups of different size can be combined by blending two or more polymers having different acid cleavable groups, such as a tert-butyl- ester group and 2-methyl-adamantyl group or an 1-ethoxy-ethoxy group and a tetrahydropyranyloxy group. A mixture of a non-crosslinked resin and a crosslinked resin may also be used. The amount of these polymers in the present invention is preferably from 30 to 99% by weight, more preferably from 50 to 98% by weight, based on the total amount of all solid components. An alkali-soluble resin or monomeric or oligomeric compound having no acid- labile groups may be further incorporated into the composition in order to control the alkali solubility.

Examples of polymer blends with polymers having different acid-labile groups are given in EP 780732, EP 679951 and US 5817444.

Preferably monomeric and oligomeric dissolution inhibitors (a2) are used in the present invention.

The monomeric or oligomeric dissolution inhibitor having the acid-labile group for use in the present invention is a compound which has at least one acid-labile group in the molecular structure, which decomposes in the presence of acid to increase the solubility₍in aqueous alkaline developer solution. Examples are alkoxymethyl ether groups, tetrahydrofuranyl ether groups, tetrahydropyranyl ether groups, alkoxyethyl ether groups, trityl ether groups, silyl ether groups, alkyl carbonate groups, trityl ester groups, silyl ester groups, alkoxymethyl ester groups, vinyl carbamate groups, tertiary alkyl carbamate groups, trityl amino groups, cumyl ester groups, acetal groups, ketal groups, tetrahydropyranyl ester groups, tetrafuranyl ester groups, tertiary alkyl ether groups, tertiary alkyl ester groups, and the like. The molecu- lar weight of the acid-decomposable dissolution inhibitive compound for use in the present invention is 3'000 or lower, preferably from 100 to 3'000, more preferably from 200 to 2'500.

Examples of monomeric and oligomeric dissolution inhibitors having acid-labile groups are described as formulae (I) to (XVI) in EP 0831369. Other suitable dissolution inhibitors having acid-labile groups are shown in US 5356752, US 5037721 , US 5015554, JP-A-1 -289946, JP-A-1 -289947, JP-A-2-2560, JP-A-3-128959, JP-A-3-158855, JP-A-3- 179353, JP-A-3- 191351 , JP-A-3-200251 , JP-A-3-200252, JP-A-3-200253, JP-A-3-200254, JP-A-3-200255, JP-A-3-259149, JA-3-279958, JP-A-3-279959, JP-A-4-1650, JP-A-4-1651 , JP-A-11260, JP- A-4-12356, JP-A-4-123567, JP-A-1 -289946, JP-A-3-128959, JP-A-3-158855, JP-A-3- 179353, JP-A-3-191351 , JP-A-3-200251 , JP-A-3-200252, JP-A-3-200253, JP-A-3-200254, JP-A-3-200255, JP-A-3-259149, JA-3-279958, JP-A-3-279959, JP-A-4-1650, JP-A-4-1651 , JP-A-11260, JP-A-4-12356, JP-A-4-12357 and Japanese Patent Applications Nos. 3-33229, 3-230790,3-320438, 4-254157, 4-52732, 4-103215, 4-104542, 4-107885, 4-107889, 4- 152195, 4-254157, 4-103215, 4-104542, 4-107885, 4-107889, and 4-152195.

The composition can also contain polymeric dissolution inhibitors, for example, polyacetals as described for example in US 5354643 or poly-N,O-acetals for example those described in US 5498506, either in combination with an alkaline soluble polymer, or in combination with a polymer containing acid labile groups which increase the solubility of the resist film in the developer after exposure, or with a combination of both types of polymers.

In the case where the dissolution inhibitor having acid-labile groups is used in the present invention in combination with the oxime derivatives of formula I, II, III, IV, V, VI or VII, the alkali-soluble polymer and/or the polymer having acid-labile groups, the amount of the dissolution inhibitor is from 3 to 55% by weight, preferably from 5 to 45% by weight, most preferably from 10 to 35% by weight, based on the total amount of all solid components of the photosensitive composition.

A polymer soluble in an aqueous alkali solution (a3) is preferably used in the present invention. Examples of these polymers include novolak resins, hydrogenated novolak resins, ace- tone-pyrogalloi resins, poly(o-hydroxystyrene), poly(m-hydroxystyrene), poly(p-hydroxystyre- ne), hydrogenated poly(hydroxystyrene)s, halogen-or alkyl-substituted poly(hydroxystyre- ne)s, hydroxystyrene/N-substituted maleimide copolymers, o/p- and m/p-hydroxystyrene co- polymers, partially o-alkylated poly(hydroxystyrene)s, [e.g., o-methylated, o-(1-methoxy)eth- ylated, o-(1-ethoxy)ethylated, o-2-tetrahydropyranylated, and o-(t-butoxycarbonyI)methylated poly(hydroxystyrene)s having a degree of substitution of from 5 to 30 mol% of the hydroxyl groups], o-acylated poly(hydroxystyrene)s [e.g., o-acetylated and o-(t-butoxy)carbonylated poly(hydroxystyrene)s having a degree of substitution of from 5 to 30mol% of the hydroxyl groups], styrene/maleic anhydride copolymers, styrene/hydroxystyrene copolymers, -meth- ylstyrene/hydroxystyrene copolymers, carboxylated methacrylic resins, and derivatives thereof. Further suitable are poly (meth)acrylic acid [e.g. poly(acrylic acid)], (meth)acrylic acid/(meth)acrylate copolymers [e.g. acrylic acid/methyl acrylate copolymers, methacrylic acid/methyl methacrylate copolymers or methacrylic acid/methyl methacrylate/t-butyl methacrylate copolymers], (meth)acrylic acid/alkene copolymers [e.g. acrylic acid/ethylene copolymers], (meth)acrylic acid/(meth)acrylamide copolymers [e.g. acrylic acid/acrylamide copolymers], (meth)acrylic acid/vinyl chloride copolymers [e.g. acrylic acid/ vinyl chloride copolymers], (meth)acrylic acid/vinyl acetate copolymer [e.g. acrylic acid/ vinyl acetate copolymers], maleic acid/vinyl ether copolymers [e.g. maleic acid/methyl vinyl ether copolymers], maleic acid mono ester/methyl vinyl ester copolymers [e.g. maleic acid mono methyl ester/methyl vinyl ether copolymers], maleic acid/(meth)acrylic acid copolymers [e.g. maleic acid/acrylic acid copolymers or maleic acid/methacrylic acid copolymers], maleic acid/(meth)acrylate copolymers [e.g. maleic acid/methyl acrylate copolymers], maleic acid/- vinyl chloride copolymers, maleic acid/vinyl acetate copolymers and maleic acid/alkene copolymers [e.g. maleic acid/ethylene copolymers and maleic acid/1 -chloropropene copolymers]. However, the alkali-soluble polymer for use in the present invention should not be construed as being limited to these examples.

Especially preferred alkali-soluble polymers (a3) are novolak resins, poly(o-hydroxystyrene), poly(m-hydroxystyrene), poly(p-hydroxystyrene), copolymers of the respective hydroxystyre- ne monomers, for example with p-vinylcyclohexanol, alkyl-substituted poly(hydroxystyrene)s, partially o- or m-alkylated and o- or m-acylated poly(hydroxystyrene)s, styrene/hydroxystyrene copolymer, and cc-methylstyrene/hydroxystyrene copolymers. The novolak resins are obtained by addition-condensing one or more given monomers as the main ingredient with one or more aldehydes in the presence of an acid catalyst.

Examples of monomers useful in preparing alkaline soluble resins include hydroxylated aromatic compounds such as phenol, cresols, i.e., m-cresol, p-cresol, and o-cresol, xylenols, e.g., 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, and 2,3-xylenol, alkoxyphenols, e.g., p-methoxy- phenol, m-methoxyphenol, 3,5-dimethoxyphenol, 2-methoxy-4-methylphenol, m-ethoxyphen- ol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol, and p-butoxyphen- ol, dialkylphenols, e.g., 2-methyl-4-isopropylphenol, and other hydroxylated aromatics including m-chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenyl- phenol, resorcinol, and naphthol. These compounds may be used alone or as a mixture of two or more thereof. The main monomers for novolak resins should not be construed as being limited to the above examples.

Examples of the aldehydes for polycondensation with phenolic compounds to obtain novola- ks include formaldehyde, p-formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, -phenylpropionaldehyde, β-phenylpropionaldehyde, o-hydroxybenzal- dehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chloro- benzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, o-methyl- benzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, p-n- butylbenzaldehyde, furfural, chloroacetaldehyde, and acetals derived from these, such as chloroacetaldehyde diethyl acetal. Preferred of these is formaldehyde. These aldehydes may be used alone or in combination of two or more thereof. Examples of the acid catalyst include hydrochloric acid, sulfuric acid, formic acid, acetic acid, and oxalic acid.

The weight-average molecular weight of the thus-obtained novolak resin suitably is from 1 '000 to 30O00. If the weight-average molecular weight thereof is lower than 1 '000, the film reduction at unexposed parts during development is liable to be large. If the weight-average molecular weight there of exceeds 50O00, the developing rate may be too low. The especially preferred range of the molecular weight of the novolak resin is from 2'000 to 20O00. The poly(hydroxystyrene)s and derivatives and copolymers thereof shown above as alkali- soluble polymers other than novolak resins each have a weight-average molecular weight of 2'000 or higher, preferably from 4'000 to 200^*000, more preferably from 5'000 to 50O00. From the standpoint of obtaining a polymer film having improved heat resistance, the weight- average molecular weight thereof is desirably at least 5'000 or higher. Weight-average molecular weight in the context of the present invention is meant to be the one determined by gel permeation chromatography and calibrated for with polystyrene standard. ln the present invention the alkali-soluble polymers may be used as a mixture of two or more thereof. In the case where a mixture of an alkali-soluble polymer and the polymer having groups which decompose by the action of an acid to enhance solubility in an alkaline developing solution is used, the addition amount of the alkali-soluble polymer is preferably up to 80% by weight, more preferably up to 60% by weight, most preferably up to 40% by weight, based on the total amount of the photosensitive composition (excluding the solvent). The amount exceeding 80% by weight is undesirable because the resist pattern suffers a considerable decrease in thickness, resulting in poor images and low resolution. In the case where an alkali-soluble polymer is used together with a dissolution inhibitor, without the polymer having groups which decompose by the action of an acid, to enhance solubility in an alkaline developing solution, the amount of the alkali-soluble polymer is preferably from 40% to 90% by weight, more preferably from 50 to 85%by weight, most preferably 60 to 80% by weight. If the amount thereof is smaller than 40% by weight, undesirable results such as reduced sensitivity are caused. On the other hand, if it exceeds 90% by weight, the resist pattern suffers a considerable decrease in film thickness, resulting in poor resolution and image reproduction.

The content of the oxime derivatives of formula I, II, III, IV, V, VI or VII, (component (b)) in the positive resist according to the present invention is preferably between 0.01% to 20% by weight, based on the total amount of all solid components in the photoresist.

The use of the oxime derivatives according to the invention in chemically amplified systems, which operates on the principle of the removal of a protecting group from a polymer, generally produces a positive resist. Positive resists are preferred over negative resists in many applications, especially because of their higher resolution. There is, however, also interest in producing a negative image using the positive resist mechanism, in order to combine the advantages of the high degree of resolution of the positive resist with the properties of the negative resist. This can be achieved by introducing a so-called image-reversal step as described, for example, in EP 361906. For this purpose, the image-wise irradiated resist material is before the developing step treated with, for example, a gaseous base, thereby image-wise neutralizing the acid which has been produced. Then, a second irradiation, over the whole area, and thermal aftertreatment are carried out and the negative image is then developed in the customary manner. Acid-sensitive components that produce a negative resist characteristically are especially compounds which, when catalysed by an acid (e.g. the acid formed during irradiation of the compounds of formulae I, II, III, IV, V, VI or VII), are capable of undergoing a crosslinking reaction with themselves and/or with one or more further components of the composition. Compounds of this type are, for example, the known acid-curable resins, such as, for example, acrylic, polyester, alkyd, melamine, urea, epoxy and phenolic resins or mixtures thereof. Amino resins, phenolic resins and epoxy resins are very suitable. Acid-curable resins of this type are generally known and are described, for example, in "Ullmann's Encyclopadie der technischen Chemie" [Ullmanns Enceclopedia of Technical Chemistry], 4th Edition, Vol. 15 (1978), p. 613 - 628. The crosslinker components should generally be present in a concentration of from 2 to 40, preferably from 5 to 30, percent by weight, based on the total solids content of the negative resist composition.

The invention thus includes, as a special embodiment, chemically amplified negative, alkali- developable photoresists, comprising (a4) an alkali-soluble resin as binder

(a5) a component that when catalysed by an acid undergoes a crosslinking reaction with itself and/or with the binder, and ι

(b) as photosensitive acid donor an oxime derivative of formula I, II, III, IV, V, VI or VII.

The composition may comprise additionally to the component (b) other photosensitive acid donors and/or (c) other additives.

Especially preferred as acid-curable resins (a5) are amino resins, such as non-etherified or etherified melamine, urea, guanidine or biuret resins, especially methylated melamine resins or butylated melamine resins, corresponding glycolurils and urones. By "resins" in this context, there are to be understood both customary technical mixtures, which generally also comprise oligomers, and pure and high purity compounds. N-hexa(methoxymethyl) melamine and tetramethoxymethyl glucoril and N,N'-dimethoxymethylurone are the acid-curable resins given the greatest preference.

The concentration of the compound of formula I, II, III, IV, V, VI or VII in negative resists in general is from 0.1 to 30, preferably up to 20, percent by weight, based on the total solids content of the compositions. From 1 to 15 percent by weight is especially preferred. Where appropriate, the negative compositions may comprise a film-forming polymeric binder (a4). This binder is preferably an alkali-soluble phenolic resin. Well suited for this purpose are, for example, novolaks, derived from an aldehyde, for example acetaldehyde or furfural- dehyde, but especially from formaldehyde, and a phenol, for example unsubstituted phenol, mono- or di-chlorosubstituted phenol, such as p-chlorophenol, phenol mono- or di-substitu- ted by C C₉alkyl, such as o-, m- or p-cresol, the various xylenols, p-tert-butylphenol, p- nonylphenol, p-phenylphenol, resorcinol, bis(4-hydroxyphenyl)methane or 2,2-bis(4-hy- droxyphenyl)propane. Also suitable are homo- and co-polymers based on ethylenically un- saturated phenols, for example homopolymers of vinyl- and 1-propenyI-substituted phenols, such as p-vinylphenol or p-(1-propenyl)phenol or copolymers of these phenols with one or more ethylenically unsaturated materials, for example styrenes. The amount of binder should generally be from 30 to 95 percent by weight or, preferably, from 40 to 80 percent by weight.

An especially preferred negative resist composition comprises from 0.5 to 15 percent by weight of an oxime derivative of formula I, II, III, IV, V, VI or VII (component (b)), from 40 to 99 percent by weight of a phenolic resin as binder (component (a4)), for example one of those mentioned above, and from 0.5 to 30 percent by weight of a melamine resin (component (a5)) as crosslinking agent, the percentages relating to the solids content of the composition. With novolak or especially with polyvinyl phenol as binder, a negative resist having especially good properties is obtained.

Oxime derivatives can also be used as acid generators, which can be activated photochemi- cally, for the acid-catalysed crosslinking of, for example, po!y(glycidyl)methacrylates in negative resist systems. Such crosslinking reactions are described, for example, by Chae et al. in Pollimo 1993, 17(3), 292.

The positive and the negative resist compositions may comprise in addition to the photosensitive acid donor compound of formula I, II, III, IV, V, VI and VII further photosensitive acid donor compounds (b1), further additives (c), other photoinitiators (d), and/or sensitizers (e). Therefore, subject of the invention also are chemically amplified resist compositions as described above, in addition to components (a) and (b), or components (a1), (a2), (a3) and (b), or components (a4), (a5) and (b) comprising further additives (c), further photosensitive acid donor compounds (b1), other photoinitiators (d), and/or sensitizers (e). Oxime derivatives of the present invention in the positive and negative resist can also be used together with other, known photolatent acids (b1), for example, onium salts, 6-nitrobenzyl- sulfonates, bis-sulfonyl diazomethane compounds, cyano group-containing oximesulfonate compounds., etc.. Examples of known photolatent acids for chemically amplified resists are described in US 5731364, US 5800964, EP 704762, US 5468589, US 5558971 , US 5558976 and particularly in EP 794457 and EP 795786.

If a mixture of photolatent acids is used in the resist compositions according to the invention, the weight ratio of oxime derivatives of formula I, II, III, IV, V, VI or VII to the other photolatent acid (b1 ) in the mixture is preferably from 1 :99 to 99:1.

Examples of photolatent acids which are suitable to be used in admixture with the compounds of formula I, II, III, IV, V, VI and VII are

(1) onium salt compounds, for example, iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts. Preferred are diphenyliodonium triflate, diphenyliodonium pyrenesulfonate, diphenyliodonium dodecylbenzenesulfonate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimona- te, diphenyliodonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, (hy- droxyphenyl)benzyImethylsulfonium toluenesulfonate and the like. Particularly preferred are triphenylsulfonium triflate, diphenyliodonium hexafluoroantimonate.

(2) halogen-containing compounds haloalkyl group-containing heterocyclic compounds, haloalkyl group-containing hydrocarbon compounds and the like. Preferred are (trichloromethyl)-s-triazine derivatives such as phen- yl-bis(trichloromethyl)-s-triazine, methozyphenyl-bis(trichloromethyl)-s-triazine, naphthyl-bis- (trichloromethyl)-s-triazine and the like; 1.1-bis(4-chlorophnyl)-2,2,2-trichloroethane; and the like.

(3) sulfone compounds, for example β-ketosulfones, β-sulfonylsulfones and their α-diazo derivatives and the like. Preferred are phenacylphenylsulfone, mesitylphenacylsulfone, bis(phenylsulfonyl)methane, bis(phenylsul- fonyl)diazomethane.

(4) sulfonate compounds, for example alkylsulfonic acid esters, haloalkylsulfonic acid esters, arylsulfonic acid esters, iminosulfonat- es, imidosulfonates and the like. Preferred imidosulfonate compounds are, for example, N- (trifluoromethlsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoro- methyIsulfonyloxy)naphthylimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(triflu- oromethylsulfonyloxy)-bicyclo-[2,2,1]-hept-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfon- yloxy)-7-oxabicyclo-[2,2,1]-hept-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)7-ox- abicyclo-[2,2,1]-hept-5-ene-2,3-dicarboximide, N-(trifluoromethyIsulfonyloxy)-bicyclo-[2,2,1]- heptan-5,6-oxy-2,3-dicarboximide, N-(camphanylsulfonyloxy) succinimide, N-(camphanylsul- fonyloxy)phthalimide, N-(camphanylsulfonyloxy)naphthylimide, N-(camphanylsuIfonyloxy)di- phenylmaleimide, N-(camphanylsulfonyloxy)bicyclo-[2,2,1]-hept-5-ene-2,3-dicarboximide, N- (camphanylsulfonyloxy)-7-oxabicyclo-[2,2,1]-hept-5-ene-2,3-dicarboximide, N-(camphanyl- sulfonyloxy)-7-oxabicyclo-[2,2,1]hept-5-ene-2,3-dicarboximide, N-(camphanylsulfonyloxy)-bi- cyclo-[2,2,1]-heptan-5,6-oxy-2,3-dicarboximide, N-(4-methylphenylsulfonyloxy)succinimide, N-(4-methylphenylsulfonyloxy)phthalimide, N-(4-methylphenylsulfonyloxy)naphthylimide, N- (4-methylphenylsulfonyloxy)naphthylimide, N-(4-methylphenylsulfonyloxy)diphenylmaleimide, N-(4-methylphenylsuIfonyloxy)-bicyclo-[2,2,1]-hept-5-ene-2,3-dicarboximide, N-(4-methylphe- nylsulfonyloxy)-7-oxabicyclo-[2,2,1]-hept-5-ene-2,3-dicarboximide, N-(4-methylphenylsulfon- yloxy)-bicyclo-[2,2,1]-heptan-5,6-oxy-2,3-dicarboximide, N-(2-trifluoromethylphenylsulfonylox- y)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)naphthylimide, N-(2-trifluoromethylphe- nylsulfonyloxy)diphenylmaleimide, N-(2-trifluoromethylphenylsulfonyloxy)-bicyclo-[2,2,1]- hept-5-ene-2,3-dicarboximide, N-(2-trif Iuoromethylphenylsulfonyloxy)-7-oxabicyclo-[2,2, 1 ]- hept-5-ene-2,3-dicarboximide, N-(2-trifluoromethylphenylsulfonyIoxy)-bicyclo-[2,2,1]-heptan- 5,6-oxy-2,3-dicarboximide and the like.

Other suitable sulfonate compounds preferably are, for example, benzoin tosylate, pyrogallol tristriflate, pyrogallolomethanesulfonic acid triester, nitorobenzyl-9,10-diethyoxyanthracene- 2-sulfonate, α-(4-toluene-sulfonyloxyimino)-benzyl cyanide, α-(4-toluene-sulfonyloxyimino)-4- methoxybenzyl cyanide, -(4-toluene-sulfonyloxyimino)-2-thienylmethyl cyanide, -(meth- anesulfonyloxyimino)-1 -cyclohexenylacetonitrile, α-(butylsulfony!oxyimino)-1 -cyclopentenyla- cetonitrile, (4-methylsulfonyloxyimino-cyclohexa-2,5-dienylidene)-phenyl-acetonitrile, (5-me- thylsulfonyloxyimino-5H-thiophen-2-ylidene)-phenyl-acetonitrile, (5-methylsulfonyloxyimino- 5H-thiophen-2-ylidene)-(2-methylphenyl)-acetonitrile, (5-propylsulfonyloxyimino-5H-thiophen- 2-ylidene)-(2-methylphenyl)-acetonitrile, (5-methylsulfonyloxyimino-5H-thiophen-2-ylidene)- (2-chlorophenyl)-acetonitrile and the like.

In the radiation sensitive resin composition of this invention, particularly preferred sulfonate compounds include pyrogallolmethanesulfonic acid triester, N-(trifluoromethylsuIfonyloxy)bi- cyclo-[2,2,1]-hept-5-ene-2,3-dicarboximide, N-(camphanylsulfonyloxy)naphthylimide, N-(2-tri- fluoromethylphenylsuIfonyloxy)phthalimide, N-(trifluoromethyIsulfonyloxy)-bicyclo-[2,2,1]- hept-5-ene-2,3-dicarboximide, N-(camphanylsulfonyloxy)naphthylimide, N-(2-trifluoromethyl- phenylsulfonyloxy)phtha!imide and the like. (5) Quinonediazide compounds, for example

1 ,2-quinonediazidesulfonic acid ester compounds of polyhydroxy compounds. Preferred are compounds having a 1 ,2-quinonediazidesulfonyl group, e.g. a 1,2-benzoquinonediazide-4- sulfonyl group, a 1 ,2-naphthoquinonediazide-4-sulfonyl group, a 1 ,2-naphthoquinonediazide- 5-sulfonyl group, a 1 ,2-naphthoquinonediazide-6-sulfonyl group or the like. Particularly preferred are compounds having a 1,2-naphthoquinonediazide-4-sulfonyl group or a 1 ,2-naphth- oquinonediazide-5-sulfonyl group. In particular suitable are 1 ,2-quinonediazidesulfonic acid esters of (poly)hydroxyphenyl aryl ketones such as 2,3,4-trihydroxybenzophenone, 2,4,6- trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',3,4-tetrahydroxybenzo- phenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone 2,2',3,4,- 4'-pentahydroxybenzophenone, 2,2'3,2,6'-pentahydroxybenzophenone, 2,3,3',4,4'5'-hexahy- droxybenzophenone, 2,3',4,4',5'6-hexahydroxybenzophenone and the like; 1 ,2-quinonediazidesulfonic acid esters of bis-[(poly)hydroxyphenyl]alkanes such as bis(4-hydroxyphe- nyl)ethane, bis(2,4-dihydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(2,4-di- hydroxyphenyl)propane, 2,2-bis-(2,3,4-tridroxyphenyl)propane and the like; 1 ,2-quinonediazidesulfonic acid esters of (poly)hydroxyphenylalkanes such as 4,4'-dihydroxytriphenylmeth- ane, 4,4'4"-trihydroxytriphenylmethane, 4,4'5,5'-tetramethyl-2,2'2"-trihydroxytriphenylmetha- ne, 2,2,5,5'-tetramethyl-4,4',4"-trihydroxytriphenylmethane, 1 ,1 ,1-tris(4-hydroxyphenyl)etha- ne, 1 ,1-bis(4-hydroxyphenyl)-1-phenylethane, 1 ,1-bis(4-hydroxyphenyl)-1-(4-[1-(hydroxyphe- nyl)-1-methylethyl]phenyl)ethane and the like; 1 ,2-quinonediazidesulfonic acid esters of (po- ly)hydroxyphenylf!avans such as 2,4,4-trimethyl-2',4',7-trihydroxy-2-phenylflavan, 2,4,4-tri- methyl-2',4',5',6,7-pentahydroxy-2-phenylflavan and the like.

The positive and negative photoresist composition of the present invention may optionally contain one or more additives (c) customarily used in photoresists in the customary amounts known to a person skilled in the art, for example, dyes, pigments, plasticizers, surfactants, flow improvers, wetting agents, adhesion promoters, thixotropic agents, colourants, fillers, solubility accelerators, acid-amplifier, photosensitizers and organic basic compounds.

Further examples for organic basic compounds which can be used in the resist composition of the present invention are compounds which are stronger bases than phenol, in particular, nitrogen-containing basic compounds. These compounds may be ionic, like, for example, tetraalkylammonium salts or non-ionic. Preferred organic basic compounds are nitrogen- containing basic compounds having, per molecule, two or more nitrogen atoms having different chemical environments. Especially preferred are compounds containing, both at least one substituted or unsubstituted amino group and at least one nitrogen-containing ring structure, and compounds having at least one alkylamino group. Examples of such preferred compounds include guanidine, aminopyridine, amino alkylpyridines, aminopyrrolidine, indazole, imidazole, pyrazole, pyrazine, pyrimidine, purine, imidazoline, pyrazoline, piperazine, amino- morpholine, and aminoalkylmorpholines. Suitable are both, the unsubstituted compounds or substituted derivatives thereof. Preferred substituents include amino, aminoalkyl groups, alkylamino groups, aminoaryl groups, arylamino groups, alkyl groups alkoxy groups, acyl groups acyloxy groups aryl groups, aryloxy groups, nitro, hydroxy, and cyano. Specific examples of especially preferred organic basic compounds include guanidine, 1,1-dimethylgu- anidine, 1 ,1 ,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2- dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2-(aminomethyl)py- ridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-am- ino-6-methylpyridine, 3-aminoehtylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N-(2-aminoethyl)piperazine, N-(2-aminoethyl)piperidine, 4-amino-2,2,6,6-tetrameth- ylpiperidine, 4-piperidinopiperidine, 2-imimopiperidine, 1-(2-aminoethyl)pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1 -p-tolylpyrazole, pyrazine, 2-(aminomethyl)-5- methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3- pyrazoline, N-aminomorpholine, and N-(2-aminoethyl)morpholine.

Other examples of suitable organic basic compounds are described in DE 4408318, US 5609989, US 5556734, EP 762207, DE 4306069, EP 611998, EP 813113, EP 611998, and US 5498506. However, the organic basic compounds suitable in the present invention are not limited to these examples.

The nitrogen-containing basic compounds may be used alone or in combination of two or more thereof. The added amount of the nitrogen-containing basic compounds is usually from 0.001 to 10 parts by weight, preferably from 0.01 to 5 parts by weight, per 100 parts by weight of the photosensitive resin composition (excluding the solvent). If the amount thereof is smaller than 0.001 part by weight, the effects of the present invention cannot be obtained. On the other hand, if it exceeds 10 parts by weight, reduced sensitivity and impaired develo- pability at unexposed parts are liable to be caused. The composition can further contain a basic organic compound which decomposes under actinic radiation ("suicide base") such as for example described in EP 710885, US 5663035, US 5595855, US 5525453, and EP 611998.

Examples of dyes (c) suitable for the compositions of the present invention are oil-soluble dyes and basic dyes, e.g. Oil Yellow #101, Oil Yellow #103, Oil Pink #312, Oil Green BG, Oil Blue BOS, Oil Blue #603, Oil Black BY, Oil Black BS, Oil Black T-505 (all manufactured by Orient Chemical Industries Ltd., Japan), crystal violet (CI42555), methyl violet (CI 42535), rhodamine B (CI 45170B), malachite green (CI 42000), and methylene blue (CI52015).

Spectral sensitizers (e) may be further added to sensitize the photo latent acid to exhibit absorption in a region of longer wavelengths than far ultaviolet, whereby the photosensitive composition of the present invention can, for example, be rendered sensitive to an i-line or g- line radiation. Examples of suitable spectral sensitizers include benzophenones, p,p'-tetra- methyldiaminobenzophenone, p_.p'-tetraethylethylaminobenzophenone, thioxanthone, 2-chlo- rothioxanthone, anthrone, pyrene, perylene, phenothiazine, benzil, acridine orange, benzo- flavin, cetoflavin T, 9,10-diphenylanthracene, 9-fIuorenone, acetophenone, phenanthrene, 2- nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4-nitroaniline, N-acetyl-p-nitro- aniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylan- thraquinone, 2-tert-butyIanthraquinone, 1 ,2-benzanthraquinone, 3-methyl-1 ,3-diaza-1 ,9-ben- zanthrone, dibenzalacetone, 1 ,2-naphthoquinone, 3-acylcoumarin derivatives, 3,3'-carbonyl- bis(5,7-dimethoxycarbonylcoumarin), 3-(aroylmethylene) thiazolines, eosin, rhodamine, ery- throsine, and coronene. However, the suitable spectral sensitizers are not limited to these examples.

These spectral sensitizers can be used also as light absorbers for absorbing the far ultraviolet emitted by a light source. In this case, the light absorber reduces light reflection from the substrate and lessens the influence of multiple reflection within the resist film, thereby diminishing the effect of standing waves.

Further suitable additives (c) are "acid-amplifiers", compounds that accelerate the acid formation or enhance the acid concentration. Such compounds may also be used in combination with the oxime derivatives of the formulae I, II, III, IV, V, VI or VII according to the invention in positive or negative resists, or in imaging systems as well as in all coating applications. Such acid amplifiers are described e.g. in Arimitsu, K. et al. J. Photopolym. Sci. Tech- nol. 1995, 8, pp 43; Kudo, K. et al. J. Photopolym. Sci. Technol. 1995, 8, pp 45; lchimura, K. et al. Chem: Letters 1995, pp 551.

Usually, for the application to a substrate of the photosensitive composition of the present invention, the composition is dissolved in an appropriate solvent. Preferred examples of these solvents include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyro- lactone, 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, propyl- ene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and tetrahydrofuran. These solvents may be used alone or as mixtures. Preferred examples of the solvents are esters, such as 2-methoxyethyl acetate, ethylene glycolmonoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl methoxypropionate, ethyl ethoxypropionate, and ethyl lactate. Use of such solvents is advantageous because the oxime derivatives represented by formulae I, II, III, IV, V, VI or VII according to the present invention have good compatibility therewith and better solubility therein.

A surfactant can be added to the solvent. Examples of suitable surfactants include nonionic surfactants, such as polyoxyethylene alkyl ethers, e.g. polyoxyethylene lauryl ether, polyoxy- ethylene stearyl ether, polyoxyethylene acetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers, e.g. polyoxyethylene, octylphenol ether and polyoxyethylene non- ylphenol ether; polyoxyethylene/polyoxypropylene block copolymers, sorbitan/fatty acid esters, e.g. sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate; fluorochemical surfactants such as F-top EF301 , EF303, and EF352 (manufactured by New Akita Chemical Company, Japan). Megafac F171 and F17.3 (manufactured by Dainippon Ink & Chemicals, Inc,. Japan), Fluorad FC 430 and FC431 (manufactured by Sumitomo 3M Ltd., Japan), Asahi Guard AG710 and Surflon S-382, SC101, SC102, SC103, SC104, SC105 , and SC106 (manufactured by Asahi Grass Col, Ltd., Japan); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd., Japan); and acrylic or methacrylic (co)polymers Poly-flow Now.75 and NO.95 (manufactured by Kyoeisha Chemical Co., Ltd., Japan). The added amount of the surfactant usually is 2 parts by weight or lower, desirably 0.5 part by weight or lower, per 100 parts by weight of the solid components of the composition of the present invention. The surfactants may be added alone or in combination of two or more thereof.

The solution is uniformly applied to a substrate by means of known coating methods, for example by spin-coating, immersion, knife coating, curtain pouring techniques, brush application, spraying and roller coating. It is also possible to apply the photosensitive layer to a temporary, flexible support and then to coat the final substrate by coating transfer (laminating).

The amount applied (coating thickness) and the nature of the substrate (coating substrate) are dependent on the desired field of application. The range of coating thicknesses can in principle include values from approximately 0.01 μm to more than 100 μm.

After the coating operation generally the solvent is removed by heating, resulting in a layer of the photoresist on the substrate. The drying temperature must of course be lower than the temperature at which certain components of the resist might react or decompose. In general, drying temperatures are in the range from 60 to 160°C.

The resist coating is then irradiated image-wise. The expression "image-wise irradiation" includes irradiation in a predetermined pattern using actinic radiation, i.e. both irradiation through a mask containing a predetermined pattern, for example a transparency, a chrome mask or a reticle, and irradiation using a laser beam or electron beam that writes directly onto the resist surface, for example under the control of a computer, and thus produces an image. Another way to produce a pattern is by interference of two beams or images as used for example in holographic applications. It is also possible to use masks made of liquid crystals that can be addressed pixel by pixel to generate digital images, as is, for example described by A. Bertsch; J.Y. Jezequel; J.C. Andre in Journal of Photochemistry and Photobiolo- gy A: Chemistry 1997, 107 pp. 275-281 and by K. P. Nicolay in Offset Printing 1997, 6, pp. 34-37.

After the irradiation and, if necessary, thermal treatment, the irradiated sites (in the case of positive resists) or the non-irradiated sites (in the case of negative resists) of the composition are removed in a manner known per se using a developer.

In order to accelerate the catalytic reaction and hence the development of a sufficient difference in solubility between the irradiated and unirradiated sections of the resist coating in the developer, the coating is preferably heated before being developed. The heating can also be carried out or begun during the irradiation. Temperatures of from 60 to 160°C are preferably used. The period of time depends on the heating method and, if necessary, the optimum period can be determined easily by a person skilled in the art by means of a few routine experiments. It is generally from a few seconds to several minutes. For example, a period of from 10 to 300 seconds is very suitable when a hotplate is used and from 1 to 30 minutes when a convection oven is used. It is important for the latent acid donors according to the invention in the unirradiated sites on the resist to be stable under those processing conditions.

The coating is then developed, the portions of the coating that, after irradiation, are more soluble in the developer being removed. If necessary, slight agitation of the workpiece, gentle brushing of the coating in the developer bath or spray developing can accelerate that process step. The aqueous-alkaline developers customary in resist technology may, for example, be used for the development. Such developers comprise, for example, sodium or potassium hydroxide, the corresponding carbonates, hydrogen carbonates, silicates or metasilicat- es, but preferably metal-free bases, such as ammonia or amines, for example ethylamine, n- propylamine, diethylamine, di-n-propylamine, triethylamine, methyl diethylamine, alkanolami- nes, for example dimethyl ethanolamine, triethanolamine, quaternary ammonium hydroxides, for example tetramethylammonium hydroxide or tetraethylammonium hydroxide. The developer solutions are generally up to 0.5 N, but are usually diluted in suitable manner before use. For example solutions having a normality of approximately 0.1 - 0.3 are well suited. The choice of developer depends on the nature of the photocurable surface coating, especially on the nature of the binder used or of the resulting photolysis products. The aqueous developer solutions may, if necessary, also comprise relatively small amounts of wetting agents and/or organic solvents. Typical organic solvents that can be added to the developer fluids are, for example, cyclohexanone, 2-ethoxyethanol, toluene, acetone, isopropanol and also mixtures of two or more of these solvents. A typical aqueous/organic developer system is based on Butylcellosolve^RTM/water.

Subject of the invention also is a process for the preparation of a photoresist by

(1 ) applying to a substrate a composition as described above;

(2) post apply baking the composition at temperatures between 60°C and 160°C;

(3) image-wise irradiating with light of wavelengths between 150 nm and 1500 nm; (4) optionally post exposure baking the composition at temperatures between 60°C and 160°C; and

(5) developing with a solvent or with an aqueous alkaline developer.

Preferred is a process, wherein the image-wise irradiation is carried out with monochromatic or polychromatic radiation in the wavelength range from 190 to 450 nm, in particular in the range from 190 to 260 nm.

The photoresist compositions can be used on all substrates and with all exposure techniques known to the person skilled in the art. For example, semiconductor substrates can be used, such as silicon, gallium arsenide, germanium, indium antimonide; furthermore substrate covered by oxide or nitride layers, such as silicon dioxide, silicon nitride, titanium nitride, silox- anes, as well as metal substrates and metal coated substrates with metals such as aluminium, copper, tungsten, etc. The substrate can also be coated with polymeric materials, for example with organic antireflective coatings, insulation layers and dielectric coatings from polymeric materials prior to coating with the photoresist.

The photoresist layer can be exposed by all common techniques, such as direct writing, i.e. with a laser beam or projection lithography in step-and repeat mode ore scanning mode, or by contact printing through a mask.

In case of projection lithography a wide range of optical conditions can be used such as coherent, partial coherent or incoherent irradiation. This includes off-axis illumination techniques, for example annular illumination and quadrupol illumination where the radiation is allowed to pass only certain regions of the lens, excluding the lens center.

The mask used to replicate the pattern can be a hard mask or a flexible mask. The mask can include transparent, semitransparent and opaque patterns. The pattern size can include also patterns which are at or below the resolution limit of the projection optics and placed on the mask in a certain way in order to modify the aerial image, intensity and phase modulation of the irradiation after having passed the mask. This includes phase shift masks and half-tone phase shift masks. The patterning process of the photoresist composition can be used to generate patterns of any desired geometry and shape, for example dense and isolated lines, contact holes, trenches, dots, etc.

The photoresists according to the invention have excellent lithographic properties, in particular a high sensitivity, and high resist transparency for the imaging radiation.

Possible areas of use of the composition according to the invention are as follows: use as photoresists for electronics, such as etching resists, electroplating resists or solder resists, the manufacture of integrated circuits or thin film transistor-resist (TFT); the manufacture of printing plates, such as offset printing plates or screen printing stencils, use in the etching of mouldings or in stereolithography or holography techniques. The coating substrates and processing conditions vary accordingly.

The compositions according to the invention are also outstandingly suitable as coating compositions for substrates of all types, including wood, textiles, paper, ceramics, glass, plastics, such as polyesters, polyethylene terephthalate, polyolefins or cellulose acetate, especially in the form of films, but especially for coating metals, such as Ni, Fe, Zn, Mg, Co or especially Cu and Al, and also Si, silicon oxides or nitrides, to which an image is to be applied by means of image-wise irradiation.

The invention relates also to the use of compounds of formula I, II, III, IV, V, VI or VII as photolatent acid donors in compositions that can be crosslinked under the action of an acid and/or as dissolution enhancers in compositions wherein the solubility is increased under the action of an acid.

Subject of the invention further is a process of crosslinking compounds that can be crosslinked under the action of an acid, which method comprises adding a compound of formula I, II, III, IV, V, VI and/or VII to the above-mentioned compounds and irradiating imagewise or over the whole area with light having a wavelength of 150-1500 nm.

The invention relates also to the use of compounds of formulae I, II, III, IV, V, VI or VII as photosensitive acid donors in the preparation of surface coatings, printing inks, printing plates, dental compositions, colour filters, resists or image-recording materials, or image- recording materials for recording holographic images, as well as to a process for the preparation of of surface coatings, printing inks, printing plates, dental compositions, colour filters, resists or image-recording materials, or image-recording materials for recording holographic images.

Subject of the invention is also the use of compounds of formulae I, II, III, IV, V, VI or VII as photosensitive acid donors in the preparation of colour filters or chemically amplified resist materials.

As already mentioned above, in photocrosslinkable compositions, oxime derivatives act as latent curing catalysts: when irradiated with light they release acid which catalyses the crosslinking reaction. In addition, the acid released by the radiation can, for example, catalyse the removal of suitable acid-sensitive protecting groups from a polymer structure, or the cleavage of polymers containing acid-sensitive groups in the polymer backbone. Other applications are, for example, colour-change systems based on a change in the pH or in the solubility of, for example, a pigment protected by acid-sensitive protecting groups.

Oxime derivatives according to the present invention can also be used to produce so-called "print-out" images when the compound is used together, with a colourant that changes colour when the pH changes, as described e.g. in JP Hei 4328552-A or in US 5237059. Such color-change systems can be used according to EP 199672 also to monitor goods that are sensitive to heat or radiation.

In addition to a colour change, it is possible during the acid-catalysed deprotection of soluble pigment molecules (as described e.g. in EP 648770, EP 648817 and EP 742255) for the pigment crystals to be precipitated; this can be used in the production of colour filters as described e.g. in EP 654711 or print out images and indicator applications, when the colour of the latent pigment precursor differs from that of the precipitated pigment crystal.

Compositions using pH sensitive dyes or latent pigments in combination with oxime derivatives can be used as indicators for electromagnetic radiation, such as gamma radiation, electron beams, UV- or visible light, or simple throw away dosimeters. Especially for light, that is invisible to the human eye, like UV- or IR-light, such dosimeters are of interest.

Finally, oxime derivatives that are sparingly soluble in an aqueous-alkaline developer can be rendered soluble in the developer by means of light-induced conversion into the free acid, with the result that they can be used as solubility. enhancers in combination with suitable film- forming resins. Resins which can be crosslinked by acid catalysis and accordingly by the photolatent acids of formula I, II, III, IV, V, VI or VII according to the invention, are, for example, mixtures of polyfunctional alcohols or hydroxy-group-containing acrylic and polyester resins, or partially hydrolysed polyvinylacetals or polyvinyl alcohols with polyfunctional acetal derivatives. Under certain conditions, for example the acid-catalysed self-condensation of acetal-functio- nalised resins is also possible.

Suitable acid-curable resins in general are all resins whose curing can be accelerated by acid catalysts, such as aminoplasts or phenolic resole resins. These resins are for example melamine, urea, epoxy, phenolic, acrylic, polyester and alkyd resins, but especially mixtures of acrylic, polyester or alkyd resins with a melamine resin. Also included are modified surface-coating resins, such as acrylic-modified polyester and alkyd resins. Examples of individual types of resins that are covered by the expression acrylic, polyester and alkyd resins are described, for example, in Wagner, Sarx, Lackkunstharze (Munich, 1971), pp. 86-123 and pp. 229-238, or in Ullmann, Encyclopadie der techn. Chemie, 4th Ed., Vol. 15 (1978), pp. 613-628, or Ullmann's Encyclopedia of Industrial Chemistry, Verlag Chemie, 1991, Vol. 18, p. 360 ff., Vol. A19, p. 371 ff..

In coating applications the surface coating preferably comprises an amino resin. Examples thereof are etherified or non-etherified melamine, urea, guanidine or biuret resins. Acid catalysis is especially important in the curing of surface coatings comprising etherified amino resins, such as methylated or butylated melamine resins (N-methoxymethyl- or N-butoxyme- thyl-melamine) or methylated/butylated glycolurils. Examples of other resin compositions are mixtures of polyfunctional alcohols or hydroxy-group-containing acrylic and polyester resins, or partially hydrolysed polyvinyl acetate or polyvinyl alcohol with polyfunctional dihydropro- panyl derivatives, such as derivatives of 3,4-dihydro-2H-pyran-2-carboxylic acid. Polysilox- anes can also be crosslinked using acid catalysis. These siloxane group-containing resins can, for example, either undergo self-condensation by means of acid-catalysed hydrolysis or be crosslinked with a second component of the resin, such as a polyfunctional alcohol, a hydroxy-group-containing acrylic or polyester resin, a partially hydrolysed polyvinyl acetal or a polyvinyl alcohol. This type of polycondensation of polysiloxanes is described, for example, in J.J. Lebrun, H. Pode, Comprehensive Polymer Science, Vol. 5, p. 593, Pergamon Press, Oxford, 1989. Other cationically polymerisable materials that are suitable for the preparation of surface coatings are ethylenically unsaturated compounds polymerisable by a cationic mechanism, such as vinyl ethers, for example methyl vinyl ether, isobutyl vinyl ether, trimeth- ylolpropane trivinyl ether, ethylene glycol divinyl ether; cyclic vinyl ethers, for example 3,4-di- hydro-2-formyl-2H-pyran (dimeric acrolein) or the 3,4-dihydro-2H-pyran-2-carboxylic acid ester of 2-hydroxymethyl-3,4-dihydro-2H-pyran; vinyl esters, such as vinyl acetate and vinyl stearate, mono- and di-olefins, such as a-methylstyrene, N-vinylpyrrolidone or N-vinylcarbaz- ole.

For certain purposes, resin mixtures having monomeric or oligomeric constituents containing polymerisable unsaturated groups are used. Such surface coatings can also be cured using compounds of formula I, II, III, IV, V, VI or VII. In that process, radical polymerisation initiators or photoinitiators can additionally be used. The former initiate polymerisation of the unsaturated groups during heat treatment, the latter during UV irradiation.

The invention also relates to a composition comprising

(b) as photosensitive acid donor, at least one compound of the formula I, II, III, IV, V, VI or VII as described above.

The compounds of formulae I, II, III, IV, V, VI or VII respectively, are generally added to the compositions in an amount from 0.1 to 30 % by weight, for example from 0.5 to 10 % by weight, especially from 1 to 5 % by weight.

According to the invention, the compounds of formula I, II, III, IV, V, VI or VII can be used together with further photosensitive acid donor compounds (b1), further photoinitiators (d), sensitisers (e) and/or additives (c).

Suitable photosensitive acid donor compounds (b1), sensitizers (e) and addtives (c) are described above.

Examples of additional photoinitiators (d) are radical photoinitiators, such as those from the class of the benzophenones, acetophenone derivatives, such as a-hydroxycycloalkylphenyl ketone, dialkoxyacetophenone, a-hydroxy- or a-amino-acetophenone, 4-aroyl-1 ,3-dioxolans, benzoin alkyl ethers and benzil ketals, monoacylphosphine oxides, bisacylphosphine oxides or titanocenes. Examples of especially suitable additional photoinitiators are: 1-(4-dodecyl- benzoyl)-1 -hydroxy-1 -methyl-ethane, 1 -(4-isopropylbenzoyl)-1 -hydroxy-1 -methyl-ethane, 1 - benzoyl-1 -hydroxy-1 -methyl-ethane, 1 -[4-(2-hydroxyethoxy)-benzoyl]-1 -hydroxy-1 -methyl- ethane, 1-[4-(acryloyloxyethoxy)-benzoyl]-1 -hydroxy-1 -methyl-ethane, diphenyl ketone, phe- nyl-1 -hydroxy-cyclohexyl ketone, (4-morpholinobenzoyl)-1 -benzyl-1 -dimethylamino-propane, 1-(3,4-dimethoxyphenyl)-2-benzyl-2-dimethyIamino-butan-1-one, (4-methylthiobenzoyl)-1- methyl-1 -morpholino-ethane, benzil dimethyl ketal, bis(cyclopentadienyl)-bis(2,6-difluoro-3- pyrryl-phenyl)titanium, trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxy-benzoyl)- (2,4,4-trimethyl-pentyl)-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-dipentyloxyphenyl- phosphine oxide or bis(2,4,6-trimethylbenzoyl)phenyl-phosphine oxide. Further suitable additional photoinitiators are to be found in US 4950581 , column 20, line 35 to column 21 , line 35. Other examples are trihalomethyltriazine derivatives or hexaarylbisimidazolyl compounds. Further examples for additional photoinitiators are borate compounds, as for example described in US 4772530, EP 775706, GB 2307474, GB 2307473 and GB 2304472. The borate compounds preferably are used in combination with electron acceptor compounds, such as, for example dye cations, or thioxanthone derivatives.

Further examples of additional photoinitiators are peroxide compounds, e.g. benzoyl peroxide (other suitable peroxides are described in US 4950581, col. 19, 1. 17-25) or cationic photoinitiators, such as aromatic sulfonium or iodonium salts, such as those to be found in US 4950581, col. 18, I. 60 to col. 19, I. 10, or cyclopentadienyl-arene-iron(ll) complex salts, for example (η⁶-isopropylbenzene)(η⁵-cyclopentadienyl)-iron(ll) hexafluorophosphate.

The surface coatings may be solutions or dispersions of the surface-coating resin in an organic solvent or in water, but they may also be solventless. Of special interest are surface coatings having a low solvent content, so-called "high solids surface coatings", and powder coating compositions. The surface coatings may be clear lacquers, as used, for example, in the automobile industry as finishing lacquers for multilayer coatings. They may also comprise pigments and/or fillers, which may be inorganic or organic compounds, and metal powders for metal effect finishes.

The surface coatings may also comprise relatively small amounts of special additives customary in surface-coating technology, for example flow improvers, thixotropic agents, leveling agents, antifoaming agents, wetting agents, adhesion promoters, light stabilisers, antioxi- dants, or sensitisers.

UV absorbers, such as those of the hydroxyphenyl-benzotriazole, hydroxyphenyl-benzophe- none, oxalic acid amide or hydroxyphenyl-s-triazine type may be added to the compositions according to the invention as light stabilisers. Individual compounds or mixtures of those compounds can be used with or without the addition of sterically hindered amines (HALS).

Examples of such UV absorbers and light stabilisers are

1. 2-(2'-Hvdroxyphenvπ-benzotriazoles. such as 2-(2'-hydroxy-5'-methylphenyl)-benzotria- zole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphenyl)- benzotriazole, 2-(2'-hydroxy-5'-(1 ,1 ,3,3-tetramethylbutyl)phenyl)-benzotriazole, 2-(3',5'-di-t- butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5- chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)-benzotriazole, 2-(2'-hydr- oxy-4'-octyloxyphenyl)-benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)-benzotriazole, 2- (3',5'-bis-(a,a-dimethylbenzyl)-2'-hydroxyphenyl)-benzotriazole, mixture of 2-(3'-tert-butyl-2'- hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-5'-[2-(2- ethyl-hexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hy- droxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2(3'-tert-butyl-2'-hydroxy- 5'-(2-methoxycarbonylethyl)phenyl)-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxy- carbonylethyl)phenyl)-benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'- hydroxyphenyl)-benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)-benzotriazole and 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenyl-benzotriazole, 2,2'-methyle- ne-bis[4-(1 ,1 ,3,3-tetramethylbutyl)-6-benzotriazol-2-yl-phenol]; transesterification product of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxy-phenyl]-benzotriazole with polyethylene glycol 300; [R-CH2CH2-COO(CH2)3]2" wherein R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzo- triazol-2-yl-phenyl.

2. 2-Hvdroxybenzophenones. such as the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4- dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy or 2'-hydroxy-4,4'-dimethoxy derivative.

3. Esters of unsubstituted or substituted benzoic acids, such as 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcin- ol, benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid octadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2-methyl-4,6-di-tert-butylphenyl ester.

4. Acrylates. such as a-cyano-b,b-diphenylacrylic acid ethyl ester or isooctyl ester, a-carbo- methoxy-cinnamic acid methyl ester, a-cyano-b-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester, a-carbomethoxy-p-methoxy-cinnamic acid methyl ester, N-(b-carbometh- oxy-b-cyanovinyl)-2-methyl-indoline.

5. Stericallv hindered amines, such as bis(2,2,6,6-tetramethyl-piperidyl)sebacate, bis(2,2,6,6- tetramethyl-piperidyl)succinate, bis(1 ,2,2,6,6-pentamethylpiperidyl)sebacate, n-butyl-3,5-di- tert-butyl-4-hydroxybenzyl-malonic acid bis(1 ,2,2,6,6-pentamethylpiperidyl) ester, condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1 ,3,5-s-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriace- tate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1 ,2,3,4-butanetetraoate, 1 ,1 '-(1 ,2-ethanediyl)- bis(3,3,5,5-tetramethyl-piperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy- 2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5- di-tert-butylbenzyl) malonate, 3-n-octyl-7J,9,9-tetramethyl-1 ,3,8-triazaspiro[4.5]decane-2,4- dione, bis(1 -octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1 -octyloxy-2,2,6,6-tetrameth- ylpiperidyl)succinate, condensation product of N,N'-bis(2,2,6,6-tetra-methyl-4-piperidyl)hexa- methylenediamine and 4-morpholino-2,6-dichloro-1 ,3,5-triazine, condensation product of 2- chloro-4,6-di(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1 ,3,5-triazine and 1 ,2-bis(3-amino- propylamino)ethane, condensation product of 2-chloro-4,6-di(4-n-butylamino-1 ,2,2,6,6-pen- tamethylpiperidyl)-1 ,3,5-triazine and 1 ,2-bis(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl- 7J,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl- 4-piperidyl)pyrrolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)-pyrrolidine- 2,5-dione.

6. Oxalic acid diamides. such as 4,4'-dioctyloxy-oxanilide, 2,2'-diethoxy-oxaniIide, 2,2'-di-oc- tyloxy-5,5'-di-tert-butyl-oxanilide, 2,2^,-didodecyloxy-5,5'-di-tert-butyl-oxanilide, 2-ethoxy-2'- ethyl-oxanilide, N,N'-bis(3-dimethylaminopropyl)oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxa- nilide and a mixture thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyl-oxanilide, mixtures of o- and p-methoxy- and of o- and p-ethoxy-di-substituted oxanilides.

7. 2-(2-HvdroxyDhenylV1 ,3.5-triazines. such as 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1 ,3,5- triazine, 2-(2-hydroxy-4-octyloxyphenyI)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-(2,4-di- hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxy- phenyl)-6-(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-meth- ylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5- triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl-phen- yl)-1 ,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimeth- ylphenyl)-1 ,3,5-triazine, 2-[4-dodecyl-/tridecyl-oxy-(2-hydroxypropyl)oxy-2-hydroxy-phenyl]- 4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine.

8. Phosphites and phosphonites, such as triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl-pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecylpenta- erythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert- butyl-4-methylphenyl)pentaerythritol diphosphite, bis-isodecyloxy-pentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis-(2,4,6-tri-tert-butylphen- yl)pentaerythritol diphosphite, tristearyl-sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)- 4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]- 1 ,3,2-dioxaphosphocine, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1 ,3,2-diox- aphosphocine, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite, bis(2,4-di-tert-butyl-6- methylphenyl)ethyl phosphite.

Such light stabilisers can also be added, for example, to an adjacent surface-coating layer from which they gradually diffuse into the layer of stoving lacquer to be protected. The adjacent surface-coating layer may be a primer under the stoving lacquer or a finishing lacquer over the stoving lacquer.

It is also possible to add to the resin, for example, photosensitisers which shift or increase the spectral sensitivity so that the irradiation period can be reduced and/or other light sources can be used. Examples of photosensitisers are aromatic ketones or aromatic aldehydes (as described, for example, in US 4017652), 3-acyl-coumarins (as described, for example, in US 4366228, EP 738928, EP 22188), keto-coumarines (as described e.g. in US 5534633, EP 538997, JP 8272095-A), styryl-coumarines (as described e.g. in EP 624580), 3-(aroylme- thylene)-thiazolines, thioxanthones, condensed aromatic compounds, such as perylene, aromatic amines (as described, for example, in US 4069954 or WO 96/41237) or cationic and basic colourants (as described, for example, in US 4026705), for example eosine, rhodanine and erythrosine colourants, as well as dyes and pigments as described for example in JP 8320551-A, EP 747771, JP 7036179-A, EP 619520, JP 6161109-A, JP 6043641, JP 6035198-A, WO 93/15440, EP 568993, JP 5005005-A, JP 5027432-A, JP 5301910-A, JP 4014083-A, JP 4294148-A, EP 359431 , EP 103294, US 4282309, EP 39025, EP 5274, EP 727713, EP 726497 or DE 2027467.

Other customary additives are - depending on the intended use - optical brighteners, fillers, pigments, colourants, wetting agents or flow improvers and adhesion promoters.

For curing thick and pigmented coatings, the addition of micro glass beads or powdered glass fibres, as described in US 5013768, is suitable.

Oxime derivatives can also be used, for example, in hybrid systems. These systems are based on formulations that are fully cured by two different reaction mechanisms. Examples thereof are systems that comprise components that are capable of undergoing an acid-catalysed crosslinking reaction or polymerisation reaction, but that also comprise further components that crosslink by a second mechanism. Examples of the second mechanism are radical full cure, oxidative crosslinking or humidity-initiated crosslinking. The second curing mechanism may be initiated purely thermally, if necessary with a suitable catalyst, or also by means of light using a second photoinitiator. Suitable additional photoinitiators are described above.

If the composition comprises a radically crosslinkable component, the curing process, especially of compositions that are pigmented (for example with titanium dioxide), can also be assisted by the addition of a component that is radical-forming under thermal conditions, such as an azo compound, for example 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), a triaze- ne, a diazosulfide, a pentazadiene or a peroxy compound, such as, for example, a hydroper- oxide or peroxycarbonate, for example tert-butyl hydroperoxide, as described, for example, in EP 245639. The addition of redox initiators, such as cobalt salts, enables the curing to be assisted by oxidative crosslinking with oxygen from the air.

The surface coating can be applied by one of the methods customary in the art, for example by spraying, painting or immersion. When suitable surface coatings are used, electrical application, for example by anodic electrophoretic deposition, is also possible. After drying, the surface coating film is irradiated. If necessary, the surface coating film is then fully cured by means of heat treatment. The compounds of formulae I, II, III, IV, V, VI or VII can also be used for curing mouldings made from composites. A composite consists of a self-supporting matrix material, for example a glass fibre fabric, impregnated with the photocuring formulation.

It is known from EP 592139 that oxime derivatives can be used as acid generators, which can be activated by light in compositions that are suitable for the surface treatment and cleaning of glass, aluminium and steel surfaces. The use of such compounds in organosilane systems results in compositions that have significantly better storage stability than those obtained when the free acid is used. The compounds of formula I, II, III, IV, V, VI or VII are also suitable for this application.

The oxime derivatives of the present invention can also be used to shape polymers that undergo an acid induced transition into a state where they have the required properties using photolithography. For instance the oxime derivatives can be used to pattern conjugated emissive polymers as described, for example, in M.L. Renak; C. Bazan; D. Roitman; Advanced materials 1997, 9, 392. Such patterned emissive polymers can be used to manufacture mi- croscalar patterned Light Emitting Diodes (LED) which can be used to manufacture displays and data storage media. In a similar way precursors for polyimides (e.g. polyimid precursors with acid labile protecting groups that change solubility in the developer) can be irradiated to form patterned polyimide layers which can serve as protective coatings, insulating layers and buffer layers in the production of microchips and printed circuit boards.

The formulations of the invention may also be used as conformal coatings, photoimagable insulating layers and dielectrics as they are used in sequential build up systems for printed circuit boards, stress buffer layers in the manufacturing of integrated circuits.

It is known that conjugated polymers like, e.g. polyanilines can be converted from semicon- ductive to conductive state by means of proton doping. The oxime derivatives of the present invention can also be used to imagewise irradiate compositions comprising such conjugated polymers in order to form conducting structures (exposed areas) embedded in insulating material (non exposed areas). These materials can be used as wiring and connecting parts for the production of electric and electronic devices. Suitable radiation sources for the compositions comprising compounds of formula I, II, III, IV, V, VI or VII are radiation sources that emit radiation of a wavelength of approximately from 150 to 1500, for example from 180 to 1000, or preferably from 190 to 700 nanometers as well as e-beam radiation and high-energy electromagnetic radiation such as X-rays. Both, point sources and planiform projectors (lamp carpets) are suitable. Examples are: carbon arc lamps, xenon arc lamps, medium pressure, high pressure and low pressure mercury lamps, optionally doped with metal halides (metal halide lamps), microwave-excited metal vapour lamps, excimer lamps, superactinic fluorescent tubes, fluorescent lamps, argon filament lamps, electronic flash lamps, photographic flood lights, electron beams and X-ray beams generated by means of synchrotrons or laser plasma. The distance between the radiation source and the substrate according to the invention to be irradiated can vary, for example, from 2 cm to 150 cm, according to the intended use and the type and/or strength of the radiation source. Suitable radiaiton sources are especially mercury vapour lamps, especially medium and high pressure mercury lamps, from the radiation of which emission lines at other wavelengths can, if desired, be filtered out. That is especially the case for relatively short wavelength radiation. It is, however, also possible to use low energy lamps (for example fluorescent tubes) that are capable of emitting in the appropriate wavelength range. An example thereof is the Philips TL03 lamp. Another type of radiation source that can be used are the light emitting diodes (LED) that emitt at different wavelengths throughout the whole spectrum either as small band emitting source or as broad band (white light) source. Also suitable are laser radiation sources, for example excimer lasers, such as Kr-F lasers for irradiation at 248 nm, Ar-F lasers at 193 nm, or F₂ laser at 157 nm. Lasers in the visible range and in the infrared range can also be used. Especially suitable is radiation of the mercury i, h and g lines at wavelengths of 365, 405 and 436 nanometers. A suitable laser-beam source is, for example, the argon-ion laser, which emits radiation at wavelengths of 454, 458, 466, 472, 478, 488 and 514 nanometers. Nd-YAG-lasers emitting light at 1064 nm and its second and third harmonic (532 nm and 355 nm respectively) can also be used. Also suitable is, for example, a helium/cadmium laser having an emission at 442 nm or lasers that emit in the UV range. With that type of irradiation, it is not absolutely essential to use a photomask in contact with the photopolymeric coating to produce a positive or negative resist; the controlled laser beam is capable of writing directly onto the coating. For that purpose the high sensitivity of the materials according to the invention is very advantageous, allowing high writing speeds at relatively low intensities. On irradiation, the oxime derivatives in the composition in the irradiated sections of the surface coating decompose to form the acids. ln contrast to customary UV curing with high-intensity radiation, with the compounds according to the invention activation is achieved under the action of radiation of relatively low intensity. Such radiation includes, for example, daylight (sunlight), and radiation sources equivalent to daylight. Sunlight differs in spectral composition and intensity from the light of the artificial radiation sources customarily used in UV curing. The absorption characteristics of the compounds according to the invention are as well suitable for exploiting sunlight as a natural source of radiation for curing. Daylight-equivalent artificial light sources that can be used to activate the compounds according to the invention are to be understood as being projectors of low intensity, such as certain fluorescent lamps, for example the Philips TL05 special fluorescent lamp or the Philips TL09 special fluorescent lamp. Lamps having a high daylight content and daylight itself are especially capable of curing the surface of a surface- coating layer satisfactorily in a tack-free manner. In that case expensive curing apparatus is superfluous and the compositions can be used especially for exterior finishes. Curing with daylight or daylight-equivalent light sources is an energy-saving method and prevents emissions of volatile organic components in exterior applications. In contrast to the conveyor belt method, which is suitable for flat components, daylight curing can also be used for exterior finishes on static or fixed articles and structures.

The surface coating to be cured can be exposed directly to sunlight or daylight-equivalent light sources. The curing can, however, also take place behind a transparent layer (e.g. a pane of glass or a sheet of plastics).

The examples which follow illustrate the invention in more detail. Parts and percentages are, as in the remainder of the description and in the claims, by weight, unless stated otherwise. Where alkyl radicals having more than three carbon atoms are referred to without any mention of specific isomers, the n-isomers are meant in each case.

1.1 : 2-Acetyloxy-1 ,3-diphenoxypropane

9.6 g (39.3 mmol) of 2-hydroxy-1 ,3-diphenoxypropane are dissolved in 80 ml of tetrahy- drofurane (THF) and cooled by an ice bath. To the solution are added dropwise 6.8 g

(86.4 mmol) of acetyl chloride and 6.0 g (59.0 mmol) of triethylamine successively. The re- action mixture is stirred at room temperature overnight, poured into 50 ml of water, and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO₄, and concentrated. The residue is purified by flash chromatography on silica gel with ethyl acetate and hexane (1:9) as eluent, yielding 5.1 g of 2-acetyloxy-1 ,3-diphenoxypropane as a colorless liquid.

4.3 g (15.0 mmol) of 2-acetyloxy-1 ,3-diphenoxypropane and 4.0 g (33.0 mmol) of 4-dimethyl- aminopyridine are mixed in 50 ml of CH₂CI₂ and cooled by an ice bath. To the solution are added dropwise 6.9 g (33.0 mmol) of trifluoroacetic anhydride, followed by 12.0 g (90.0 mmol) of AICI₃ by portions. The reaction mixture is stirred at room temperature overnight, poured into ice water, and extracted with CH₂CI₂. The organic phase is washed with water, dried over MgSO₄, and concentrated. The residue is purified by recrystallization from a mixture of toluene and hexane (1:1), yielding 5.98 g of the product as a pale yellow solid with a melting point (mp.) of 108-109°C.

5.8 g (12.1 mmol) of the compound of example 1.2 are dissolved in 60 ml of ethanol. To the solution are added 2.9 g (42.4 mmol) of hydroxylammonium chloride and 8.8 ml (108.9 mmol) of pyridine. The reaction mixture is refluxed for 4 hours, and the solvent is distilled off by a rotary evaporator. The residue is poured into water, and extracted with ethyl acetate. The organic phase is washed with potassium hydrogen sulfate aqueous solution, water, and brine, dried over MgSO₄. After the MgSO₄ is removed by filtration, 0.61 g of cone. HCI is added to the solution and stirred at room temperature for 3 hours. The reaction mixture is washed with water and brine, dried over MgSO₄, and concentrated. The residue is purified by recrystallization from toluene, yielding 3.98 g of the compound of example 1.3 as a white solid with a melting point of 135-138°C.

2.0 g (3.93 mmol) of the compound of example 1.3 are dissolved in 10 ml of THF and cooled in an ice bath. To the solution are added 1.23 g (8.65 mmol) of 1 -propanesulfonyl chloride, followed by dropwise addition of 1.19 g (11.8 mmol) of triethylamine. The reaction mixture is stirred for 2.5 hours at 0°C, poured into ice water, and extracted with ethyl acetate. The organic phase is washed with 0.1 N HCI and water, dried over MgSO₄, and concentrated. The residue is purified by flash chromatography on silica gel with ethyl acetate and hexane (1 :3) as eluent, yielding 2.42 g (3.36 mmol; 85 %) of the compound of example 1.4 as a colorless liquid. The structure is confirmed by the ¹H-NMR spectrum (CDCI₃). δ [ppm]: 1.10 (t, 6H), 1.88-1.98 (m, 4H), 2.13 (s, 3H), 3.39 (t, 4H), 4.30 (d, 4H), 5.48-5.55 (m, 1H), 7.04 (d, 4H), 7.52 (d, 4H). The spectrum indicates that the compound is a single isomer, which is tentatively assigned as Z, Z-conformation.

._ . _.

Example 2:

1.9 g (3J4 mmol) of the compound of example 1.3 are dissolved in 10 ml of methanol. To the solution are added 0.77 g (5.61 mmol) of potassium carbonate, dissolved in 2 ml of water. The reaction mixture is stirred at room temperature for 2.5 hours, poured into water, and extracted with ethyl acetate. The organic phase is washed with water, dried over MgSO₄, and concentrated, yielding 1.57 g of the crude product as a white solid with a melting point of 167-169°C. This crude product is used in the next reaction step without further purification.

2.84 g (6.1 mmol) of the compound of example 2.1 are dissolved in 15 ml of THF and cooled in an ice bath. To the solution are added 1J4 g (12.2 mmol) of 1 -propanesulfonyl chloride, followed by dropwise addition of 1.85 g (18.3 mmol) of triethylamine. The reaction mixture is stirred for 1 hour at 0°C and for 30 min at room temperature, poured into water, and extracted with ethyl acetate. The organic phase is washed with 0.1 N HCI and water, dried over MgSO₄, and concentrated. The residue is purified by flash chromatography on silica gel with ethyl acetate and methylene chloride (1 :20) as eluent, yielding 2.33 g (3.43 mmol; 56 %) of the compound of example 2.1 as a colorless liquid. The structure is confirmed by the ¹H- NMR spectrum (CDCI₃). δ [ppm]: 1.10 (t, 6H), 1.88-1.98 (m, 4H), 2.56 (d, 1 H), 3.40 (t, 4H), 4.19-4.26 (m, 4H), 4.43-4.47 (m, 1H), 7.04 (d, 4H), 7.53 (d, 4H). The spectrum indicates that the compound is a single isomer, which is tentatively assigned as Z, Z-conformation.

^EaaύΛS

2.84 g (6.1 mmol) of the compound of example 2.1 are dissolved in 15 ml of THF and cooled in an ice bath. To the solution are added 1.74 g (12.2 mmol) of 1 -propanesulfonyl chloride, followed by dropwise addition of 1.85 g (18.3 mmol) of triethylamine. The reaction mixture is stirred for 1 hour at 0°C and for 30 min at room temperature, poured into water, and extracted with ethyl acetate. The organic phase is washed with 0.1 N HCI and water, dried over MgSO₄, and concentrated. The residue is purified by flash chromatography on silica gel with ethyl acetate and methylene chloride (1 :20) as eluent, yielding 0J5 g (0.96 mmol; 16 %) of the compound of example 3 as a colorless liquid. The structure is confirmed by the ¹H-NMR spectrum (CDCI₃). δ [ppm]: 1.05-1.13 (m, 9H), 1.88-1.99 (m, 6H), 3.23 (t, 2H), 3.40 (t, 4H), 4.37-4.41 (m, 4H), 5.25-5.30 (m, 1H), 7.04 (d, 4H), 7.53 (d, 4H). The spectrum indicates that the compound is a single isomer, which is tentatively assigned as Z, Z-conformation.

4.1 :

5.2 g (20 mmol) of tris(2-hydroxyethyl)isocyanurate, 75.2 g (0.80 mol) of phenol and 1.0 g (5.3 mmol) of p-toluenesulfonic acid are dissolved in 30 ml of xylene. The reaction mixture is refluxed overnight, and xylene and the excess amount of phenol are removed by a distillation under reduced pressure. To the residue is added water and extracted with ethyl acetate. The organic phase is washed with water, dried over MgSO₄, and concentrated. The residue is purified by recrystallization from toluene, yielding 8.36 g of the product of example 4.1 as a white solid with a melting point of 115-119°C.

7.0 g (13.9 mmol) of the compound of example 4.1 and 5.6 g (45.9 mmol) of 4-dimethylamin- opyridine are mixed in 100 ml of CH₂CI₂ and cooled by ice bath. To the solution are added dropwise 9.6 g (45.9 mmol) of trifluoroacetic anhydride, followed by 8.5 g (139 mmol) of AICI₃ by portions. The reaction mixture is stirred at room temperature overnight, poured into ice water, and extracted with CH₂CI₂. The organic phase is washed with water, dried over MgSO₄, and concentrated, yielding 9.52 g of the product of example 4.2 as a pale yellow viscous solid. This crude product is used in the next reaction step without further purification.

9.9 g (12.5 mmol) of example 4.2 are dissolved in 80 ml of ethanol. To the solution are added 3.1 g (45.0 mmol) of hydroxylammonium chloride and 8.9 g (112.5 mmol) of pyridine. The reaction mixture is refluxed overnight, and the solvent is distilled off by a rotary evaporator. The residue is poured into water, and extracted with ethyl acetate. The organic phase is washed with potassium hydrogen sulfate aqueous solution, water, and brine, dried over MgSO and concentrated. The residue is dissolved in 50 ml of ethyl acetate and 0.63 g of cone. HCI is added to the solution and stirred at room temperature for 2 hours. The reaction mixture is washed with water and brine, dried over MgSO , and concentrated. The residue is washed in 50 ml of toluene at 100°C for 15 min. After cooling to room temperature, the solid is isolated by a filtration and washed with toluene. The product (9.45 g) of example 4.3 is obtained as a white solid with a melting point of 154-160°C.

3.0 g (3.65 mmol) of the compound of example 4.3 are dissolved in 20 ml of THF and cooled in an ice bath. To the solution are added 1.7 g (12.0 mmol) of 1 -propanesulfonyl chloride, followed by dropwise addition of 1.7 g (16.4 mmol) of triethylamine. The reaction mixture is stirred for 2 hours at 0°C, poured into ice water, and extracted with ethyl acetate. The organic phase is washed with 0.1 N HCI and water, dried over MgSO₄, and concentrated. The residue is purified by recrystallization from ethanol, yielding 3.27 g (2.87 mmol; 79 %) of the compound of example 4.4 as a white solid with a melting point of 110-122°C. The structure is confirmed by the ¹H-NMR spectrum (CDCI₃). δ [ppm]: 1.10 (t, 9H), 1.87-1.97 (m, 6H), 3.38 (t, 6H), 4.28 (t, 6H), 4.38 (t, 6H), 6.97 (d, 6H), 7.48 (d, 6H). The spectrum indicates that the compound is a single isomer, which is tentatively assigned as Z, Z, Z-conformation.

Example 5:

5.1 : Sodium 2-phenoxyethanesulfonate

To a solution of Na₂SO₃ (12.9 g, 102.3 mmol) in 100 mL of water is added β-chlorophenetole (15.3 g, 97.4 mmol), and the mixture is stirred at 120°C for 24 h. Cooling the mixture affords white precipitates, which are collected by filtration and dried in vacuo. The product is obtained as a white solid in 87% yield. The structure is confirmed by ¹H-NMR spectrum (DMSO-d₆). δ [ppm]: 2.88 (t, 2H), 4.18 (t, 2H), 6.88-6.93 (m, 3H), 7.24-7.29 (m, 2H). 5.2: Tetra-n-butylammonium 2-phenoxyethanesulfonate

To a solution of sodium 2-phenoxyethanesulfonate (7.88 g, 35.1 mmol) in 50 mL of water are added tetra-π-butylammonium bromide (11.3 g, 35.1 mmol) and 50 mL of CH₂CI₂ successively, and then the mixture is stirred at room temperature overnight. The CH₂CI₂ phase is separated and dried over MgSO₄. Evaporation of the solution yields the product as colorless oil. The structure is confirmed by ¹H-NMR spectrum (CDCI₃). δ [ppm]: 1.01 (t, 12H), 1.45 (dt, 8H), 1.60-1.69 (m, 8H), 3.26-3.34 (m, 10H), 4.46 (t, 2H), 6.88-6.96 (m, 3H), 7.22-7.29 (m, 2H).

To a solution of tetra-n-butylammonium 2-phenoxyethanesulfonate (15.6 g, 35.1 mmol) and 4-dimethylaminopyridine (4J2 g, 38.6 mmol) in 200 mL of CH₂CI₂ are added trifluoroacetic anhydride (5.37 mL, 38.6 mmol) dropwise and AICI₃ (25J g, 193 mmol) by portions successively with cooling by an ice bath. The mixture is stirred at room temperature overnight, and then poured into ice-water. The CH₂CI₂ phase is separated, washed with water, and dried over MgSO₄. Evaporation of the solution yields the product as slightly yellowish oil. The structure is confirmed by ¹H-NMR spectrum (CDCI₃). δ [ppm]: 1.02 (t, 12H), 1.46 (dt, 8H), 1.62-1.71 (m, 8H), 3.27-3.38 (m, 10H), 4.58 (t, 2H), 7.05 (d, 2H), 8.02 (d, 2H).

To a solution of the compound of example 5.3 (14.0 g, 25.9 mmol) in 20 mL of ethanol is added a solution of NH₂OH HCI (2.16 g, 31.1 mmol) and sodium acetate (3.61 g, 44.0 mmol) in 20 mL of water. The mixture is stirred at 90°C overnight, and then poured into water. The product is extracted with CH₂CI₂ two times, washed with brine, and dried over MgSO₄. Evaporation of the solution yields the product as slightly yellowish oil. The structure is confirmed by ¹H-NMR spectrum (CDCI₃). δ [ppm]: 1.00 (t, 12H), 1.43 (dt, 8H), 1.60-1.72 (m, 8H), 3.28 (t, 8H), 3.37 (t, 2H), 4.44 (t, 2H), 6.92 (d, 2H), 7.44 (d, 2H). The hydrogen atom of the oxime moiety is not observed.

To a solution of the compound of example 5.4 (1.09 g, 1.96 mmol) in 10 mL of THF are added triethylamine (0.41 mL, 2.94 mmol) and 2-naphthalenesulfonyl chloride (0.53 g, 2.35 mmol). The mixture is stirred at room temperature overnight, and then poured into water. The product is extracted with CH₂CI₂ two times, washed with water, dried over MgSO₄, and concentrated. The residue is purified by column chromatography on silica-gel with CH₂CI₂ and EtOH (95:5) as eluent. The product is obtained as colorless oil. The structure is confirmed by ¹H-NMR spectrum (CDCI₃). δ [ppm]: 1.01 (t, 12H), 1.46 (dt, 8H), 1.62-1.73 (m, 8H), 3.27-3.36 (m, 10H), 4.52 (t, 2H), 7.01 (d, 2H), 7.41 (d, 2H), 7.66 (dd, 1H), 7.71 (dd, 1H), 7.92-7.97 (m, 2H), 8.00-8.05 (m, 2H), 8.61 (s, 1 H).

Example 6: (c₄H₉)_{4 To a so}|_{ution 0}f the compound of example 5.4 (1.66 g, 3.0 mmol) in 10 ml of CH₂CI₂ are added triethylamine (0.63 ml, 4.5 mmol) and 1 -propanesulfonyl chloride (0.41 ml, 3.6 mmol). The mixture is stirred at room temperature for 2 hours, and then is poured into water. The product is extracted with CH₂CI₂ two times, washed with water, dried over MgSO₄, and concentrated. The residue is purified by flash chromatography on silica gel with CH₂CI₂ and ethanol (95:5 to 90:10) as eluent, yielding 1J9 g (90 %) of the product as slightly yellowish viscous oil. The structure is confirmed by ¹H-NMR spectrum (CDCI₃). δ [ppm]: 1.01 (t, 12H), 1.10 (t, 3H), 1.45 (tq, 8H), 1.61-1.71 (m, 8H), 1.87-1.98 (m, 2H), 3.26-3.40 (m, 12H), 4.51-4.55 (m, 2H), 7.04 (d, 2H), 7.50 (d, 2H).

Example 7: 1 -0 g (1.22 mmol) of the compound of example 4.3 and 0.64 ml (5.49 mmol) of 2,6-lutidine are dissolved in 8 ml of CH₂CI₂ and cooled in an ice bath. To the solution is added 0J2 ml (4.39 mmol) of trifluoromethanesulfonic anhydride. After the reaction mixture is stirred for 1 hour at 0°C and poured into 1 N HCI, the crude product is extracted with ethyl acetate. The organic phase is washed with 1 N HCI and water, dried over MgSO₄, and concentrated. The residue is purified by flash chromatography on silica gel with n-hexane and ethyl acetate (80:20 to 50:50) as eluent, yielding 1.16 g (78 %) of the product as a white solid with a melting point of 47-49°C. The structure is confirmed by the ¹H-NMR spectrum (CDCI₃). δ [ppm]: 4.31 (t, 6H), 4.40 (t, 6H), 7.01 (d, 6H), 7.45 (d, 6H). The spectrum indicates that the compound is a single isomer, which is tentatively assigned as Z, Z, Z-conformation.

Exampl

9.5 g (38.9 mmol) of 2-hydroxy-1 ,3-diphenoxypropane and 3.6 g (23.3 mmol) of succinyl chloride are dissolved in 50 ml of THF and cooled by an ice bath. To the solution are added 7.1 g (58.4 mmol) of 4-dimethylaminopyridine and stirred at room temperature overnight. The reaction mixture is poured into 0.1 N HCI aqueous solution and extracted with ethyl acetate. The organic phase is washed with water, dried over MgSO₄, and concentrated. The residue is purified by recrystallization from toluene, yielding 5.67 g of the product of example 8.1 as a white solid with a melting point of 101-104°C.

8.2: 5.6 g (9.8 mmol) of the com-

pound of example 8.1 and 5.3 g (43.2 mmol) of 4-dimethylaminopyridine are mixed in 100 ml of CH₂CI₂ and cooled by an ice-salt bath. To the solution are added dropwise 9.1 g (43.2 mmol) of trifluoroacetic anhydride, followed by 15.7 g (118 mmol) of AICI₃ by portions. The reaction mixture is stirred at room temperature overnight, poured into ice water, and extracted with CH₂CI₂. The organic phase is washed with water, dried over MgSO₄, and concentrated. The residue is purified by recrystallization from toluene, yielding 7.93 g of the product of example 8.2 as an orange solid with a melting point of 171-174°C.

8.3: 5 g (5.24 mmol) of the

compound of example 8.2 are dissolved in 50 ml of ethanol. To the solution are added 1.75 g (25.1 mmol) of hydroxylammonium chloride and 4.97 g (62.9 mmol) of pyridine. The reaction mixture is refluxed for 3 hours, and the solvent is distilled off by a rotary evaporator. The residue is poured into water, and extracted with ethyl acetate. The organic phase is washed with 1 N HCI solution, water, and brine, and dried over MgSO₄. After removing MgSO₄, 0.27 g of cone. HCI is added to the solution and stirred at room temperature for 2 hours. The reaction mixture is washed with water and brine, dried over MgSO₄, and concentrated. The residue is purified by flash chromatography on silica gel with ethyl acetate and hexane (1 :2) as eluent, yielding 3.4 g of the product of example 8.3 as a white solid with a melting point of 191-196°C.

1.84 g (1.81 mmol) of the compound of example 8.3 are dissolved in 15 ml of THF and cooled in an ice bath. To the solution are added 1.64 g (11.5 mmol) of 1 -propanesulfonyl chloride, followed by dropwise addition of 1.10 g (10.9 mmol) of triethylamine. The reaction mixture is stirred for 2 hours at room temperature, poured into ice water, and extracted with ethyl acetate. The organic phase is washed with 0.1 N HCI and water, dried over MgSO₄, and concentrated. The residue is purified by flash chromatography on silica gel with ethyl acetate and hexane (1:2) as eluent, yielding 1.60 g (1.11 mmol; 61 %) of the compound of example 8.4 as a white solid with a melting point of 43-49°C. The structure is confirmed by the ¹H-NMR spectrum (CDCI₃). δ [ppm]: 1.10 (t, 12H), 1.92 (m, 8H), 2.71 (s, 4H), 3.38 (t, 8H), 4.31 (d, 8H), 5.52 (m, 2H), 7.02 (d, 8H), 7.51 (d, 8H). The spectrum indicates that the compound is a single isomer, which is tentatively assigned as Z, Z, Z, Z-conformation.

Exam_ple 9- xampⁱe a.

1.40 g (1.38 mmol) of the compound of example 8.3 are dissolved in 15 ml of THF and cooled in an ice bath. To the solution are added 1.38 g (6.54 mmol) of 4-chlorobenzenesul- fonyl chloride, followed by dropwise addition of 0.84 g (8.28 mmol) of triethylamine. The reaction mixture is stirred overnight at room temperature, poured into water, and extracted with ethyl acetate. The organic phase is washed with 0.1 N HCI and water, dried over MgSO , and concentrated. The residue is purified by recrystallization from 2-propanol, yielding 2.14 g (1.25 mmol; 91 %) of the compound of example 9 as a white solid with a melting point of 62-68°C. The structure is confirmed by the ¹H-NMR spectrum (CDCI₃). δ [ppm]: 2J2 (s, 4H), 4.32 (d, 8H), 5.51 (m, 2H), 7.01 (d, 8H), 7.44 (d, 8H), 7.57 (d, 8H), 7.94 (d, 8H). The spectrum indicates that the compound is a single isomer, which is tentatively assigned as Z, Z, Z, Z-conformation.

Example 10

A chemically amplified positive resist formulation is prepared by mixing the following components:

100.00 parts of a resin binder (a copolymer of 22 mol-% of styrene, 69 mol-% of p-hydroxy- styrene and 9 mol-% of t-butyl acrylate, having a Mw of 9850; ^RTMMaruzen MARUKA LYNCUR PHS/STY/TBA, provided by Maruzen Oil Company, Japan) 0.48 parts of a levelling agent (FC-430, provided by 3M) 475.00 parts of propylene glycol methyl ether acetate (PGMEA) (provided by Tokyo Kasei, Japan)

4.0 parts of the photoacid generator to be tested The resist formulation is spin coated onto a hexamethyl dimethylsilazane-treated silicone wafer at 3000 rpm for 45 seconds and softbaked for 90 seconds at 140°C on a hotplate to obtain a film thickness of 800 nm. The resist film is then exposed to deep UV radiation of 254 nm wavelength through a narrow band interference filter and a multidensity quartz mask using an Ushio's high pressure mercury lamp, UXM-501MD, and a mask aligner Canon PLA- 521. The samples then are post exposure baked for 90 seconds at 140°C on a hotplate and developed. The exposure intensity is measured with a Unimeter UIT-150 from Ushio. The Dose to Clear (E₀), which is the dose just sufficient to completely remove the resist film with 60 seconds immersion development in 1.79 % aqueous tetramethyl ammonium hydroxide developer is determined from the measured contrast curve. The smaller the required dose the more sensitive is the resist formulation. The results are collected in Table 1 and demonstrate that the compositions are suitable for the preparation of positive photoresists. Table 1

Example 11 :

The degradation point (Td) of the photolatent acid generator compound in the presence of the same amount (with respect to the weight) of poly(4-hydroxystyrene), which has a Mw of 5100 and is commercially available under the trade name of ^RTMMaruzene MARUKA LYNCUR PHMC from Maruzene Oil Company of Tokyo, Japan, is determined by DSC analysis (Differential Scanning Calorimetry). The higher the values, the more thermostable are the tested photolatent acid compounds. The results are summarized in the table 2 below.

Table 2

Claims

Patent Claims

1. A chemically amplified photoresist composition comprising

wherein

R is C C₁₈alkylsulfonyI, C_rC₁₀haloalkylsulfonyl, camphorylsulfonyl, phenyl-C_rC₃alkylsuI- fonyl, C₃-C₁₂cycIoalkylsulfonyl, phenylsulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl, wherein the groups cycloalkyl, phenyl, naphthyl, anthracyl and phenanthryl of the radicals C₃-C₁₂cycloalkylsulfonyl ,phenyI-CrC₃alkylsulfonyl, phenylsulfonyl, naphthylsulfonyl, anthracylsulfonyl and phenanthrylsulfonyl are unsubstituted or substituted by one or more halogen, C_rC haloalkyl, CN, NO₂, C_rC₁₆alkyl, phenyl, C_r C₄alkylthio, OR , (CO)OR₇, C₁-C₄alkyl-(CO)O-, R₇OSO₂- and/or -NR₅R₆; or R^ is C₂-

C₆haloalkanoyl, halobenzoyl, or a group ;

XL X₂ and X₃ independently of each other are O or S;

R₂ is halogen or CrCι₀haloalkyl;

R₃ is phenylenedisulfonyl, naphthylenedisulfonyl, _> ^di" phenylenedisulfonyl, or oxydiphenylenedisulfonyl, wherein these radicals are unsubstituted or substituted by C C₁₂alkyl; or R₃ is C₂-C₁₂alkylenedisulfonyl;

A is a direct bond, unsubstituted Cι-C₁₂alkylene, CrC^alkylene which is substituted by C₃- C₃₀cycloalkyl; or A is C₃-C₃₀cycloalkylene, C_rC₈haloalkylene, C₂-C ₂alkenylene, C₄-C₈- cycloalkenylene, C₆-C₁₂bicycloalkenylene; or An is phenylene, which is unsubstituted or substituted by one or more C_rC₁₂alkyl, C C₄haloalkyl, phenyl-C_rC₃-alkyl, halogen, phenyl, OR₄, NR₅R₆, SR₇, SOR₇, and/or SO₂R₇, optionally the substituents OR₄, SR₇ and NR₅R₆ form 5- or 6-membered rings, via the radicals R₄, R₅, R₆ and/or R₇, with further substituents on the phenylene ring or with one of the carbon atoms of the phenylene ring; or An is naphthylene, anthracylene or phenanthrylene ring, wherein the radicals naphthylene, anthracylene and phenanthrylene are unsubstituted or substituted by C C₆alkyl, phenyl, OR , NR₅R₆, SR₇, SOR₇, and/or SO₂R₇, optionally the substituents OR₄, SR₇ and NR₅R₆ form 5- or 6-membered rings, via the radicals R₄, R₅. R₆ and/or R₇ with further substituents on the naphthylene, anthracylene or phenanthrylene ring or with one of the carbon atoms of the naphthylene, anthracylene or phenanthrylene ring; or A is a heteroarylene ring which is unsubstituted or substituted by C Cealkyl, phenyl, OR₄, NR₅R₆, SR₇, SOR₇, and/or SO₂R₇, optionally the substituents OR₄, SR₇ and NR ₅R₆ form 5- or 6-membered rings, via the radicals R₄, R₅, R₆ and/or R₇ with further substituents on the heteroarylene ring or with one of the carbon atoms of the heteroarylene ring; wherein all radicals A optionally additionally are substituted by a group having a -O-C-bond or a -O-Si-bond which cleaves upon the action of an acid;

Ai, A₂, A3, j, A₅, A., A₇, A3, A₉, A10, An and A_t2 independently of each other are a direct bond, -O-, -S-, -NR₄-, -CO-, -O(CO)-, -S(CO)-, -NR₄(CO)-, -SO-, -SO₂-, or -OSO₂-; or Ai, A₂, A₃, A₄, A₅, A₆, A₇, A₈, A₉, A₁₀, An and A₁₂ are d-C₁₂alkylene or phenylene wherein these radicals are unsubstituted or substituted by one or more C C₁₂alkyl, C

C₄haloalkyl, halogen, OR₄ and/or SR₇; i is C_rCι₂alkylene which is substituted by OR , SR₇, halogen and/or phenyl; or Y^ is C₂-

C₁₂alkylene, which is interrupted by one or more -O-, -S-, -NR₄-, -O(CO)-, -S(CO)-,

-NR₄(CO)-, -SO-, -SO₂- and/or -OSO₂-, and the radical C₂-C₁₂alkylene being substituted by OR₄, SR₇, halogen and/or phenyl; Y₂ is a trivalent radical of C Cι₂alkylene, phenylene, naphthylene, or a heterocyclic ring wherein these radicals are unsubstituted or substituted by CrC₁₂alkyl, halogen, OR₄ and/or SR₇; i i O or Y₂ ιs — N — , — P — or — p — ;

Y₃ is a tetravalent radical of C C₁₂alkylene, phenylene, naphthylene, or a heterocyclic ring wherein these radicals are unsubstituted or substituted by CrC₁₈alkyl, halogen, OR₄ and/or SR₇;

X is halogen;

R is hydrogen, C_rC_1aalkyi which is unsubstituted or substituted by phenyl, OH, C C₁₂. alkoxy, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR₅R₆, C Cι₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl and/or by C₂-C₆alkanoyl; or R₄ is C₂-Cι₈alkyl which is interrupted by one or more -O-, and which is unsubstituted or substituted by phenyl, OH, CrC^alkoxy, C₂-Cι₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR₅R₆, CrC^alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl and/or by C₂-C₆alkanoyl; or R₄ is phenyl which is unsubstituted or substituted by OH, C_rC₁₈aIkyl, halogen and/or C Cι₂alkoxy; or R₄ is C₂-Cι₈alkanoyl which is unsubstituted or substituted by phenyl, OH, C Cι₂alkoxy, C₂- C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR₅R₆, C C₁₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)suIfonyl, and/or by C₂-C₆alkanoyl; or R₄ is C_rC₁₈alkylsulfonyI which is unsubstituted or substituted by phenyl, OH, C_rCι₂al- koxy, C₂-Cι₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR₅R_6l CrC₁₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl, and/or by C₂-C₆alk- anoyl; or R₄ is phenylsulfonyl which is unsubstituted or substituted by one or more halogen, C₁-C₄haloalkyl, CN, NO₂, C C₁₆alkyl, phenyl, C C alkylthio, C_rC₁₂alkoxy and/or phenoxy; or R₄ is benzoyl, CrC₁₀haloalkylsulfonyl, camphorylsulfonyl, phenyl- CrC₃alkylsulfonyl, C₃-C₁₂cycloalkylsulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl;

R₅ and R₆ independently of each other are hydrogen or C_rC₁₈alkyl which is unsubstituted or substituted by OH, C C₄alkoxy, C₂-Cι₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, phenylamino, phenylaminocarbonyl, C_rC₁₂alkylsulfonyl, phenylsulfonyl, (4-methyl-phenyl)sulfonyl and/or C C₆alkanoyl; or R₅ and R₆ are C₂- C₁₈alkyl which is interrupted by one or more -O-, and which is unsubstituted or substituted by OH, C C₄alkoxy, C₂-Cι₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, phenylamino, phenylaminocarbonyl, CrC^alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl and/or C C₆alkanoyl; or R₅ and R₆ are phenyl which is unsubstituted or substituted by OH, C_rC₁₈alkyl, halogen and/or Cι-Cι₂alkoxy; or R₅ and R₆ are C₂-C₁₈alkanoyl, which is unsubstituted or substituted by phenyl, OH, C C₁₂- alkoxy, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, phenylamino, phenylaminocarbonyl, C_rC₁₂alkylsulfonyl, phenylsulfonyl, (4- methylphenyl)sulfonyl, and/or by C₂-C₆alkanoyl; or R₅ and R₆ are C C₁₈alkylsulfonyl which is unsubstituted or substituted by phenyl, OH, C_rC₁₂alkoxy, C₂-C₁₂alkoxycarbonyI, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, phenylamino, phenylaminocarbonyl, C C₁₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl, and/or by C₂- C₆alkanoyI; or R₅ and R₆ are phenylsulfonyl which is unsubstituted or substituted by one or more halogen, C C₄haloalkyl, CN, NO₂, C C₁₆alkyl, phenyl, C C₄alkylthio, C_r C₁₂alkoxy and/or phenoxy; or R₅ and R₆ are benzoyl, C_rC₁₀haloalkylsulfonyl, camphorylsulfonyl, phenyl-C_rC₃alkylsulfonyl, C₃-C₁₂cycloalkylsulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl; or R₅ and R₆, together with the nitrogen atom to which they are attached, form a 5-, 6- or 7-membered ring which may be interrupted by - O- or by -NR₄-;

R₇ is hydrogen, phenyl, C_rC₁₈alkyl which is unsubstituted or substituted by phenyl, OH, C_r C₁₂alkoxy, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR₅R₆, C Cι₂aIkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl, and/or by C₂- C₆alkanoyl; or R₇ is C₂-C₁₈alkyl which is interrupted by one or more -O- and which is unsubstituted or substituted by phenyl, OH, C C₁₂alkoxy, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR₅R₆, C C₁₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl, and/or by C₂-C₆alkanoyI; or R₇ is C₂- C₁₈alkanoyl which is unsubstituted or substituted by phenyl, OH, C_rC₁₂alkoxy, C₂- C₁₂alkoxycarbonyI, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR₅R₆, C Cι₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl, and/or by C₂-C₆alkanoyl; or R₇ is C_rC₁₈alkylsulfonyl which is unsubstituted or substituted by phenyl, OH, Cι- C₁₂alkoxy, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR₅R₆, CrC^alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl, and/or by C₂-C₆alkanoyl; or R₇ is phenylsulfonyl which is unsubstituted or substituted by one or more halogen, C_rC₄haloalkyl, CN, NO₂, Cι-C₁₆alkyl, phenyl, CrC₄alkylthio, C C₁₂alkoxy and/or phenoxy; or R₇ is benzoyl, Cι-Cιohaloalkylsulfonyl, camphorylsulfonyl, phenyl- Cι-C3alkylsulfonyl, C₃-C₁₂cycloalkylsulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl;

R₈, R₉ and Rι₀ independently of one another are CrC₆alkyl which is unsubstituted or substituted by halogen; or R₈, R₉ and R₁₀ are phenyl which is unsubstituted or substituted by C_rC₄alkyl or halogen; or R₉ and R₁₀ together are 1 ,2-phenylene or C₂-C₆alkylene which is unsubstituted or substituted by C C₄alkyl or halogen;

Ar'-, is C_rC₁₂alkyl which is unsubstituted or substituted by C₃-C₃₀cycloalkyl; or Ar^ is C₃- C₃₀cycloalkyl, C_rC₈haloalkyl, C₂-C₁₂alkenyl, C₄-C₈cycloalkenyl, C₆-C₁₂bicycloalkenyl, camphoryl; or Ar'i is phenyl, which is unsubstituted or substituted by one or more CrCealkyl, C_rC₄haloalkyl, phenyl-CrC₃-alkyl, halogen, phenyl, OR'₄, NR'₅R'₆, SR'₇, SOR'₇, and/or SO₂R'₇, optionally the substituents OR'₄, SR'₇ and NR'₅R'₆ form 5- or 6-membered rings, via the radicals R'₄, R'₅, R'₈ and/or R'₇, with further substituents on the phenyl ring or with one of the carbon atoms of the phenyl ring; or Ar'₁ is naphthyl, anthracyl or phenanthryl, wherein the radicals naphthyl, anthracyl and phenanthryl are unsubstituted or substituted by C_rC₆alkyl, phenyl, OR'₄, NR'₅R'₆, SR'₇₍ SOR'_7l and/or SO₂R'₇, optionally the substituents OR'₄, SR'₇ and NR'₅R'₆ form 5- or 6-membered rings, via the radicals R'4, R'₅, R'e and /or R'₇ with further substituents on the naphthyl, anthracyl or phenanthryl ring or with one of the carbon atoms of the naphthyl, anthracyl or phenanthryl ring; or Ar'i is a heteroaryl radical which is unsubstituted or substituted by CrCealkyl, phenyl, OR'₄ , NR'sR'e, SR'₇, SOR'_7> and/or SO₂R'₇, optionally the substituents OR'₄, SR'₇ and NR'sR'e form 5- or 6-membered rings, via the radicals R'₄₎ R'₅₎ R'e and/or R'₇ with further substituents on the heteroaryl ring or with one of the carbon atoms of the heteroaryl ring;

and wherein the radicals C C₁₂alkyl, phenyl, naphthyl, anthracyl, phenanthryl or the het- o eroaryl radical optionally are substituted by 1 to 3 of the groups groups s— O ⁺ _> O Q ^R15 ^R ₂o

— O— S n— 0^"M⁺ , — C II— O -M ₊ ⁺ , — + Ni — R₁₆ , L- , — + s 1— R₂₁ L and/or O R₁₇

— I— ₂₃ L^" ; and wherein all radicals Ar^ optionally additionally are substituted by a group having a - O-C-bond or a -O-Si-bond which cleaves upon the action of an acid;

Ar' is phenylene, naphthylene, ( )^~CH2^~( _ ) , diphenylene or oxydi-

phenylene, wherein these radicals are unsubstituted or substituted by C_rC₁₂alkyl; or

Ar' is C C₁₂alkylene or — \__ ^D_D~D \__/ — '_* wherein all radicals

Ar"! optionally are substituted by 1 to 3 of the groups groups _> o ff ₊ ^R15 _ ₊ R₂₀

— O— S— 0-M⁺ , — C— 0-M⁺ , — N— R₁₆ L _f — s— R₂₁ L and/or O R₁₇

— "— R₂₃ ^~ ; and wherein all radicals Ar"_! optionally additionally are substituted by a group having a - O-C-bond or a -O-Si-bond which cleaves upon the action of an acid;

D is -O-, -S-, -NRV, -CO-, -O(CO)-, -S<CO)-, -NR'₄(CO)-, -SO-, -SO₂-, or -OSO₂-;

D-i is C_rCι₂alkylene or C₂-C₁₂alkylene, which is interrupted by one or more -O-, -S-, -NR' -, -CO-, -O(CO)-, -S(CO)-, -NR'₄(CO)-, -SO-, -SO₂-, and/or -OSO₂; and wherein the radicals CrC₁₂alkylene and C₂-C₁₂alkylene optionally are substituted by 1 to 3 of the groups

groups L

+ — and/or — I — ₂₃ ;

R'₄ is hydrogen, C_rC₁₈alkyl which is unsubstituted or substituted by phenyl, OH, C C₁₂alkoxy, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR'sR'e, C C₁₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)suIfonyl and/or by C₂-C₆alkanoyl; or R'₄ is C₂-Cι₈alkyl which is interrupted by one or more -O-, and which is unsubstituted or substituted by phenyl, OH, C Cι₂alkoxy, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR'₅R'₆, CrCι₂alkylsuIfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyI and/or by C₂-C₆alkanoyl; or R'₄ is phenyl which is unsubstituted or substituted by OH, CrCι₈alkyl, halogen and/or C_rCι₂alkoxy; or R'₄ is C₂-Cι₈alkanoyl which is unsubstituted or substituted by phenyl, OH, CrC₁₂alkoxy, C₂- C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR'sR'e, CrC₁₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl, and/or by C₂-C₆alkanoyl; or R' is CrC₁₈alkylsulfonyl which is unsubstituted or substituted by phenyl, OH, Cι-C₁₂. alkoxy, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR'sR'e, CrC₁₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl, and/or by C₂-C₆alkanoyl; or R' is phenylsulfonyl which is unsubstituted or substituted by one or more halogen, C_rC haloalkyl, CN, NO₂, CrC₁₆alkyl, phenyl, C C₄alkylthio, C C₁₂alkoxy and/or phenoxy; or R'₄ is benzoyl, CrC₁₀haloalkylsuIfonyl, camphorylsulfonyl, phenyl- CrC₃alkylsulfonyI, C₃-C₁₂cycloalkyIsulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl; and wherein the radicals CrC₁₈alkyl, C₂-C₁₈alkyl, phenyl, C₂-C₁₈alkanoyl, phenylsulfonyl, benzoyl, Cι-C₁₀haloalkylsulfonyl, camphorsulfonyl, phenyl-Cr C₃alkylsulfonyl, C₃-C₁₂cycloalkylsulfonyI, naphthylsulfonyl, anthracylsulfonyl or phe-

nanthrylsulfonyl optionally are substituted by 1 to 3 of the groups groups _>

R₂₁ L and/or

— I— R₂₃ L ;

R'₅ and R'₆ independently of each other are hydrogen or CrC₁₈alkyl which is unsubstituted or substituted by OH, CrC alkoxy, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, phenylamino, phenylaminocarbonyl, C C₁₂alkyl- sulfonyl, phenylsulfonyl, (4-methyl-phenyl)sulfonyl and/or C_rC₆alkanoyI; or R'₅ and R'₆ are C₂-C₁₈alkyl which is interrupted by one or more -O-, and which is unsubstituted or substituted by OH, CrC₄alkoxy, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, phenylamino, phenylaminocarbonyl, d-C^alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl and/or CrC₆alkanoyl; or R'₅ and R'₆ are phenyl which is unsubstituted or substituted by OH, C_rC₁₈alkyl, halogen and/or C C₁₂alkoxy; or R'₅ and R'₆ are C₂-C₁₈alkanoyl, which is unsubstituted or substituted by phenyl, OH, C_rC₁₂alkoxy, C₂-Cι₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, phenylamino, phenylaminocarbonyl, C Cι₂alkylsulfonyI, phenylsulfonyl, (4- methylphenyl)sulfonyl, and/or by C₂-C₆alkanoyl; or R'₅ and R'₆ are C_rCι₈alkylsulfonyl which is unsubstituted or substituted by phenyl, OH, C C ₂alkoxy, C₂-C₁₂alkoxycarbonyI, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, phenylamino, phenylaminocarbonyl, CrCι₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl, and/or by C₂- C₆alkanoyl; or R'₅ and, R'₆ are phenylsulfonyl which is unsubstituted or substituted by one or more halogen, C C haloalkyl, CN, NO₂, Cι-C₁₆alkyl, phenyl, CrC₄alkylthio, C C₁₂alkoxy and/or phenoxy; or R'₅ and R'₆ are benzoyl, d-Ciohaloalkylsulfonyl, camphorylsulfonyl, phenyl-CrC₃alkylsulfonyl, C₃-C₁₂cycloalkylsulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl; or R'₅ and R'₆₎ together with the nitrogen atom to which they are attached, form a 5-, 6- or 7-membered ring which may be interrupted by - O- or by -NR' -; and wherein the radicals C₁-C₁₈alkyl, C₂-Cι₈alkyl, phenyl, C₂- C₁₈aIkanoyl, CrC₁₈alkylsulfonyl, phenylsulfonyl, benzoyl, d-Ciohaloalkylsulfonyl, cam- phorsulfonyl, phenyl-CrC₃alkylsulfonyl, C₃-Cι₂cycloalkylsulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl optionally are substituted by 1 to 3 of the groups

groups L , — S— R₂₁ L

+ .- and/or 1 — R₂₃ L ;

R'₇ is hydrogen, phenyl, C_rC₁₈alkyl which is unsubstituted or substituted by phenyl, OH, C_rC₁₂alkoxy, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR'sR'e, C C₁₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)suIfonyl, and/or by C₂-C₆alkanoyl; or R'₇ is C₂-C₁₈alkyl which is interrupted by one or more -O- and which unsubstituted or substituted by phenyl, OH, C₁-C₁₂alkoxy, C₂- C₁₂aIkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR'sR'e, C_rCι₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl, and/or by C₂-C₆alkanoyl; or R'₇ is C₂-C₁₈aIkanoyl which is unsubstituted or substituted by phenyl, OH, C C₁₂alkoxy, C₂-C₁₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR'sR'e, C C₁₂alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl, and/or by C₂-C₆alkanoyl; or R'₇ is CrCι₈alkylsulfonyl which is unsubstituted or substituted by phenyl, OH, C C₁₂alkoxy, C₂-Cι₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR'sR'e, C C₁₂alkylsulfonyl, phenylsulfonyl, (4- methylphenyI)sulfonyl, and/or by C₂-C₆alkanoyl; or R'₇ is phenylsulfonyl which is unsubstituted or substituted by one or more halogen, CrC haloalkyl, CN, NO₂, CrCι₆aIkyl, phenyl, CrC₄alkylthio, C C₁₂alkoxy and/or phenoxy; or R'₇ is benzoyl,

CrCiohaloalkylsulfonyl, camphorylsulfonyl, phenyl-CrC₃alkylsulfonyl, C₃-

C₁₂cycloalkylsulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl; and wherein the radicals Cι-C₁₈alkyl, C₂-Cι₈alkyl, C₂-Cι₈alkanoyl, CrCι₈alkylsulfonyl, phenylsulfonyl, benzoyl, d-Ciohaloalkylsulfonyl, camphorsulfonyl, phenyI-CrC₃alkylsuIfonyl, C₃-C₁₂cycIoalkylsulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl op-

tionally are . substituted by 1 to 3 of the groups _>

— C— 0^'M⁺ , — N— R₁₆ L _f — S— R₂₁ L and/or —I— R₂₃ L^~ _;

^R17 provided that at least one of the by

1 to 3 groups , _t

^R ₂o — S— R₂₁ L^~ and/or — I— R₂₃ L^~ ;

^R15 ^R ₂1

M⁺ is R₁₈— N— R₁₆ , R₂₀— S— R₂₂ , R₂₄— I— R_{23 )} Li⁺, Na⁺, K⁺, Cs⁺, 1/2Mg²⁺, 1/2Ca²⁺ or

^R17

1/2Ba²⁺;

L^" is F^", CI^", Br^", I^", HSO₄ ^", 1/2SO₄ ^2", NO₃ ^", o^~ , B(R₁₉) ^',

CIO₄ ^", BF₄ ^", PF₆ ^', AsF₆ ^" or SbF₆ ^";

Ri5, ie, R17 and R₁₈ independently of each other are hydrogen or phenyl which is unsubstituted or substituted by one or more C_rC₁₂alkyl, halogen, -NO₂, -CN, phenyl, C_rC₄- alkoxy, hydroxy, C₂-Cι₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, C₁-C₄alkylthio, phenylthio, C₂-Cι₂alkanoyl, C₂-Cι₂alkanoyloxy, benzoyl and/or benzoyloxy; or R₁₅, Rie, Rι₇ and R₁₈ are C_rCι₂ alkyl, C₂-Cι₂alkyl which is interrupted by one or more -O-, and wherein the radicals CrCι₂ alkyl and C₂-Cι₂alkyl are unsubstituted or substituted by one or more halogen, hydroxy, -NO₂, -CN, phenyl, C₂-Cι₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, CrC₄alkylthio, phenylthio, C₂-C ₂alkanoyl, C₂-Cι₂alkanoyloxy, benzoyl and/or benzoyloxy; or R₁₅ and Rι₆, if appropriate together with CrC₂alkylene, -O-, -S-, or -CO-, form fused ring; or Rι₅ and R₁₆, if appropriate together with CrC₂alkylene, -O-, -S-, or - CO-, form a 5-, 6-, or 7-membered ring;

Rι₉ is phenyl, which is unsubstituted or substituted by one or more CrCealkyl, halogen, -NO₂, -CN, phenyl, CrC₄alkoxy, C₂-C ₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, C_r C₄alkylthio, phenylthio, C₂-Cι₂alkanoyl, C₂-C₁₂alkanoyloxy, benzoyl, benzoyloxy; or R₁₉ is CrC₁₂alkyl, or C₂-Cι₂alkyl which is interrupted by one or more -O-, wherein the radicals CrCealkyl, and C₂-Cι₂alkyl are unsubstituted or substituted by one or more halogen, hydroxy, -NO₂, -CN, phenyl, C₂-Cι₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, C_r C₄alkylthio, phenylthio, C₂-Cι₂alkanoyl, C₂-C₁₂alkanoyloxy, benzoyl and/or benzoyloxy;

R₂₀, R₂₁ and R₂₂ independently of each other are phenyl, which is unsubstituted or substituted by one or more d-Cι₂ alkyl, halogen, -NO₂, -CN, phenyl, CrC₄alkoxy, hydroxy, C₂- Cι₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, C_rC₄alkylthio, phenylthio, C₂- C ₂alkanoyl, C₂-Cι₂alkanoyloxy, benzoyl and/or benzoyloxy; or R₂₀, R_2i and R₂₂ independently of each other are C_rCι₂ alkyl, C₂-Cι₂alkyl which is interrupted by one or more -O-, and wherein the radicals C Cι₂ alkyl and C₂-Cι₂alkyl are unsubstituted or substituted by one or more halogen, hydroxy, -NO₂, -CN, phenyl, C₂-Cι₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, C C alkylthio, phenylthio, C₂-Cι₂alkanoyl, C₂- Cι₂alkanoyloxy, benzoyl and/or benzoyloxy; or R₂₀ and R₂ι, if appropriate together with C C₂alkylene, -O-, -S-, or -CO-, form a fused ring; or R₂o and R₂ , if appropriate together with CrC₂alkylene, -O-, -S-, or -CO-, form a 5-, 6-, or 7-membered ring; and

R₂₃ and R₂₄ independently of each other are phenyl, which is unsubstituted or substituted by one or more of CrCealkyl, halogen, -NO₂, -CN, phenyl, CrC alkoxy, hydroxy, C₂- Cι₂alkoxycarbonyl, phenoxy, phenoxycarbonyl, CrC₄alkylthio, phenylthio, C₂-C₁₂- alkanoyl, C₂-Cι₂alkanoyloxy, benzoyl and/or benzoyloxy; or R₂₃ and R₂₄, if appropriate together with CrC₂alkylene, -O-, -S-, or -CO-, form fused ring.

2. A chemically amplified photoresist composition according to claim 1 comprising compounds of the formula I, II, III, IV or V, wherein

Ri is C_rCι₈aIkylsulfonyl, C Cιohaloalkylsulfonyl, camphorylsulfonyl, phenyl-CrC₃alkylsul- fonyl, phenylsulfonyl or naphthylsulfonyl, wherein the groups phenyl and naphthyl of the radicals phenyl-CrC₃alkylsulfonyl, phenylsulfonyl and naphthylsulfonyl are unsubstituted or substituted by one or more halogen, C Cι₆alkyl or C C₄alkoxy;

R₂ is fluorine;

Ari is phenylene;

Ai, A₂, A₃, A», A₅, Ae, A₇, Ag, A₉, A₁₀, An and A₁₂ independently of each other are a direct bond, -O-, -S- or -O(CO)-; or Ai, A₂, A₃₎ A₄, A₅₎ A₆, A₇, A₈, A₉, Aio, An and A_i2 are d- Cι₂alkylene or phenylene;

Yi is CrCι₂alkylene which is substituted by OR₄;

Y₂ is a trivalent radical of CrCι₂alkyIene, phenylene or heterocyclic ring ;

Y₃ is a tetravalent radical of CrCι₂alkylene;

X is fluorine;

R₄ is hydrogen, phenyl, CrCι₈alkyl, C₂-Cι₈alkanoyl, benzoyl, CrCi₈alkylsulfonyl, C Cιo- haloalkylsulfonyl, camphorylsulfonyl, phenyl-CrC₃alkylsulfonyl, phenylsulfonyl or naphthylsulfonyl, wherein the groups phenyl and naphthyl of the radicals phenyl-C C₃- alkylsulfonyl, phenylsulfonyl and naphthylsulfonyl are unsubstituted or substituted by one or more halogen, CrCι₆aIkyl or C C alkoxy.

3. A chemically amplified photoresist composition according to claim 1 comprising compounds of the formula I, II, IV or V, wherein

Ri is CrCι₈alkylsulfonyI, Ci-Ciohaloalkylsulfonyl, naphthylsulfonyl or phenylsulfonyl which is unsubstituted or substituted by halogen, wherein ;

R₂ is halogen;

An is phenylene;

Ai, A₂, A3, !, As, Ae, A₇, As, A₉, Aι₀, An and A₁₂ independently of each other are a direct bond, -O-, O(CO) or C_rCi₂alkylene;

Yi is CrCi₂alkylene which is substituted by OR ; or Yi is C₂-Cι₂alkylene, which is interrupted by -OSO₂-;

Y₂ is a trivalent radical of CrCι₂alkylene or a trivalent heterocyclic ring;

X is halogen;

R₄ is hydrogen or C₂-Cι₈alkanoyl;

Ar'i is phenyl, which is unsubstituted or substituted by OR'₄; o

R' is CrCι₈alkyl which is unsubstituted or substituted by — s— O^"M⁺ ;

0

R15, Rie, R₁7 and R₁₈ are hydrogen or CrCealkyl.

4. A chemically amplified photoresist composition according to claim 1 , which is a positive resist.

5. A chemically amplified positive photoresist composition according to claim 4, comprising (a1 ) at least one polymer having an acid-labile group which decomposes in the presence of an acid to increase the solubility in aqueous alkaline developer solution; and/or

(a2) at least one monomeric or oligomeric dissolution inhibtor having an acid-labile group which decomposes in the presence of an acid to increase the solubility in aqueous alkaline developer solution; and/or

(a3) at least one alkali-soluble monomeric, oligomeric or polymeric compound; and

(b) as photosensitive acid donor, at least one compound of formula I, II, III, IV, V, VI or VII.

6. A chemically amplified photoresist composition according to claim 1 , which is a negative resist.

7. A chemically amplified negative photoresist composition according to claim 6, comprising (a4) an alkali-soluble resin as binder;

(a5) a component which, when catalysed by an acid undergoes a crosslinking reaction with itself and/or with the binder; and

(b) as photosensitive acid donor, at least one compound of formula I, II, III, IV, V, VI and VII.

8. A chemically amplified photoresist composition according to anyone of claims 1-7, in addition to components (a) and (b), or components (a1), (a2), (a3) and (b), or components (a4), (a5) and (b) comprising further additives (c), further photosensitive acid donor compounds (b1), other photoinitiators (d), and/or sensitizers (e).

9. A process for the preparation of a photoresist by

(1 ) applying to a substrate a composition according to claim 1 ;

(2) post apply baking the composition at temperatures between 60°C and 160°C; (3) image-wise irradiating with light of wavelengths between 150 nm and 1500 nm;

(4) optionally post exposure baking the composition at temperatures between 60°C and 160°C; and

(5) developing with a solvent or with an aqueous alkaline developer.

10. A compound of the formula I, II, III, IV, V, VI and VII as defined in claim 1.

11. A process for the specific preparation of the thermally stable isomer of the oxime ester compounds of formula I, II, III, IV, V, VI and VII according to claim 1 by (1) treating the isomeric mixture of the corresponding free oxime compounds of formula I', II', III', IV, V or VI' , obtained by conventional methods,

wherein Ri, R₂, R₃, X, An, An', An", A_1t A₂, A₃, A₄, A₅, A₆, A₇, A₈, A₉, Aι₀, An, A_i2, Yi, Y₂ and Y₃ are as defined in claim 1 , with an acid; and (2) reacting the thus prepared single isomeric free oxime compound with the corresponding acid halides or acid anhydrides of formula XV, XVI or XVII

R CI (XV), R₁-O-R₁ (XVI), CI-R₃-CI (XVII).

12. A composition comprising

(b) as photosensitive acid donor, at least one compound of the formula I, II, III, IV, V, VI or VII according to claim 10.

13. Use of compounds of formula I, II, III, IV, V, VI or VII according to claim 10 as photosensitive acid donors in compositions that can be crosslinked under the action of an acid and/or as dissolution enhancers in compositions wherein the solubility is increased under the action of an acid.

14. Process for crosslinking compounds that can be crosslinked under the action of an acid, which method comprises adding a compound of formula I, II, III, IV, V, VI and/or VII according to claim 10 to the above-mentioned compounds and irradiating imagewise or over the whole area with light having a wavelength of 150-1500 nm.

15. Process according to claim 14 for the preparation of surface coatings, printing inks, printing plates, dental compositions, colour filters, resists, or image-recording materials, or image-recording materials for recording holographic images.

Summary

New oxime sulfonate compounds of the formula I, II, III, IV, V, VI and VII

Ar,' wherein

Ri is for example C_rCι₈alkylsulfonyl, R₂ is halogen or CrCiohaloalkyl; R₃ is for example unsubstituted or substituted phenylenedisulfonyl, diphenylenedisulfonyl, or oxydi- phenylenedisulfonyl; An is for example a direct bond, C Cι₂alkylene; -O-C-bond or a -O- Si-bond which cleaves upon the action of an acid; Ai, A₂, A₃, A₄, A₅, A₆, A₇, A₈, A₉, Aio, An and Aι₂ are for example a direct bond, -O-, or -S-, or are Cι-Cι₂alkylene or phenylene unsubstituted or substituted; Yi is C_rCι₂alkylene which is for example substituted by OR₄, or SR₇; Y₂ is e.g. a trivalent radical of C_rCι₂alkylene; Y₃ is e.g. a tetravalent radical of C_r C_i2alkylene; X is halogen; Ar'i is for example CrCealkyl which is unsubstituted or substituted; Ar"ι is for example phenylene; provided that at least one of the radicals Ar'i, Ar"ι,

is substituted by 1 to 3 groups of

example halogen; Rι₅, Rι₆, R₁7 and R ₈ e.g. hydrogen or phenyl; Rι₉, R₂₀₍ R21, R2₂ and R₂₃ are e.g. phenyl; are especially suitable for the preparation of photoresists.