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    • 专利摘要:
    Compounds of Formula 1, Formula 2 and Formula 3 of the present invention are well suited as photosensitive acid donors in chemically amplified resist formulations. [Formula 1] [Formula 2] [Formula 3] In the above formula, R 1 is, for example, hydrogen, C 1 -C 12 alkyl, C 3 -C 30 cycloalkyl, C 2 -C 12 alkenyl, C 4 -C 8 cycloalkenyl, substituted or unsubstituted phenyl, substituted or Unsubstituted, naphthyl, anthracyl or phenanthryl, substituted or unsubstituted heteroaryl radicals; Wherein all radicals of R 1 except hydrogen may be further substituted by groups having —OC— bonds or —O—Si— bonds which decompose upon the action of an acid; R ' 1 is, for example, substituted or unsubstituted, phenylene, naphthylene, diphenylene or oxydiphenylene; R 2 is halogen or C 1 -C 10 haloalkyl; R 3 is, for example, substituted or unsubstituted C 1 -C 18 alkylsulfonyl, phenylsulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl, or R 3 is, for example, C 2- C 6 haloalkanoyl or halobenzoyl; R ' 3 is, for example, substituted or unsubstituted, phenylenedisulfonyl, naphthylenedisulfonyl, diphenylenedisulfonyl or oxydiphenylenedisulfonyl; X is halogen.
    公开号:KR20000063080A
    申请号:KR1020000016548
    申请日:2000-03-30
    公开日:2000-10-25
    发明作者:아사쿠라도시카게；야마토히토시；오와마사키；비르바움요안-루크；디트리커쿠르트；다나베쥰이치
    申请人:에프. 아. 프라저, 에른스트 알테르 (에. 알테르), 한스 페터 비틀린 (하. 페. 비틀린), 피. 랍 보프, 브이. 스펜글러, 페. 아에글러；시바 스페셜티 케미칼스 홀딩 인크.；
    IPC主号:
    专利说明:

    Oxime derivatives and the use thereof as latent acids
    The present invention relates to a novel oxime derivative, a chemically amplified photoresist composition comprising the compound and the use of the compound as latent acid, which can be activated by actinic radiation and irradiation with an electron beam.
    US Pat. No. 45,40598 describes a composition for surface dyes comprising a photosensitive oxime sulfonate compound, for example 4-chloro-α-trifluoroacetophenone oxime benzenesulfonate and a conventional acid-curable resin. US Pat. No. 4736055 = EP # 199672 describes the preparation of polymers in which 2,2,2-trifluoro-1-phenyl-ethanone oxime-O- (4-hydroxyphenylsulfonate) can be used as a resin in positive photoresists. It is described as an ingredient. US Pat. No. 56,27011 and US Pat. No. 5759740 both EP = 571330 disclose α as catalysts in positive and negative photoresists, chemically amplified for wavelengths in the irradiation region of mercury i-rays (365 nm). The use of-(4-toluene-sulfonyloxyimino) -4-methoxybenzyl cyanide and α- (4-toluene-sulfonyloxyimino) -3-thienylmethyl cyanide is described. GB # 2306958 reports the use of oxime-sulfonate as a latent donor in positive and negative photoresists for wavelengths in the irradiation region exceeding 180 to 600 nm, in particular 390 nm. US 5714625 describes non-aromatic α- (alkylsulfonyloxyimino) -1-cyclohexenylacetonitrile and α- (alkylsulfonyloxyimino) -1-cyclopentenylacetonitrile. EP 241423 describes the use of oxime sulfonate compounds in concentrations of about 25% as photocatalyst generators in nonchemically amplified positive resists. Chemical Abstracts No. 97: 144503, 78: 97752, Synthesis (1995), 553 describe some fluoroketoxime sulfonate compounds as experimental products for synthetic studies.
    The art is thermally and chemically stable and is activated by light, UV-irradiation, X-ray irradiation or electron beam and then various acid-catalyzed reactions such as polycondensation reactions, acid-catalyzed desorption There is a need for reactive non-ionic latent acid donors that can be used as a catalyst for polymerization, acid-catalyzed protonic substitution or acid-catalyzed removal of protective groups.
    Surprisingly, it has now been found that certain oxime derivatives described below are particularly suitable as catalysts for the acid catalyzed reactions mentioned above. The optical absorption spectrum of certain compounds of the invention can be adjusted over a wide range of electromagnetic spectra and is particularly suitable for applications in a wide UV range. Moreover, chemically amplified photoresist compositions comprising the oxime derivatives of the present invention are thermally stable at high baking temperatures even during processing and provide high luminous flux.
    Therefore, the present invention
    (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) a chemically amplified photoresist composition comprising at least one compound of formula 1, formula 2 or formula 3 as a photosensitive acid donor.

    In the above formula,
    R 1 is hydrogen; Unsubstituted C 1 -C 12 alkyl; C 1 -C 12 alkyl substituted with C 3 -C 30 cycloalkyl; R 1 is C 3 -C 30 cycloalkyl, C 1 -C 8 haloalkyl, C 2 -C 12 alkenyl, C 4 -C 8 cycloalkenyl, C 6 -C 12 bicycloalkenyl, camphoryl; Unsubstituted or one or more radicals C 1 -C 12 -alkyl, C 1 -C 4 -haloalkyl, phenyl-C 1 -C 3 -alkyl, halogen, phenyl, OR 4 , NR 5 R 6 , SR 7 , SOR 7 and / or phenyl substituted by SO 2 R 7 , and optionally the substituents OR 4 , SR 7 and NR 5 R 6 together with the further substituents on the phenyl ring or one carbon atom of the phenyl ring, represent radicals R 4 , R 5 , To form a 5- or 6-membered ring via R 6 and / or R 7 ; R 1 is naphthyl, anthracyl or phenanthryl unsubstituted or substituted by C 1 -C 6 alkyl, phenyl, OR 4 , NR 5 R 6 , SR 7 , SOR 7 and / or SO 2 R 7 , Optionally the substituents OR 4 , SR 7 and NR 5 R 6 together with further substituents on the naphthyl, anthracyl or phenanthryl ring or the radical R 4 , R 5, R together with one carbon atom of the naphthyl, anthracyl or phenanthryl ring To form a 5- or 6-membered ring via 6 and / or R 7 ; Or R 1 is a heteroaryl radical unsubstituted or substituted with C 1 -C 6 alkyl, phenyl, OR 4 , NR 5 R 6 , SR 7 , SOR 7 and / or SO 2 R 7 , optionally substituted with OR 4 , SR 7 and NR 5 R 6 form a 5- or 6-membered ring via the radicals R 4 , R 5 , R 6 and / or R 7 together with one carbon atom of an additional substituent or heteroaryl ring on the heteroaryl ring To; Wherein all radicals R 1 except hydrogen may be optionally substituted by a group having an —OC— bond or —O—Si— bond which decomposes upon the action of an acid;
    R ' 1 is unsubstituted or substituted with C 1 -C 12 alkyl phenylene, naphthylene, , Diphenylene or oxydiphenylene, or R ' 1 is C 1 -C 12 alkylene or Is;
    A is -O-, -S-, -NR 4- , -O (CO)-, -S (CO)-, -NR 4 (CO)-, -SO-, -SO 2 -or -OSO 2- ego;
    A 1 is C 1 -C 12 alkylene or C 2 -C 12 alkylene blocked by one or more -O-;
    R 2 is halogen or C 1 -C 10 haloalkyl;
    R 3 is C 1 -C 18 alkylsulfonyl, C 1 -C 10 haloalkylsulfonyl, camphorylsulfonyl, phenyl-C 1 -C 3 alkylsulfonyl, C 3 -C 12 cycloalkylsulfonyl, phenylsulfonyl , Naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl, wherein the radical C 3 -C 12 cycloalkylsulfonyl, phenyl-C 1 -C 3 alkylsulfonyl, phenylsulfonyl, naphthylsulfonyl, anthracylsulfonyl And the group cycloalkyl, phenyl, naphthyl, anthracyl and phenanthryl of phenanthrylsulfonyl are unsubstituted or substituted with one or more halogen, C 1 -C 4 haloalkyl, CN, NO 2 , C 1 -C 16 alkyl, phenyl , Substituted by C 1 -C 4 alkylthio, OR 4 , COOR 7 , C 1 -C 4 alkyl- (OC) O—, R 7 OSO 2 — and / or —NR 5 R 6 ; Or R 3 is C 2 -C 6 haloalkanoyl, halobenzoyl, or a group or ego;
    Y 1 , Y 2 and Y 3 are each independently O or S;
    R ' 3 is phenylenedisulfonyl, naphthylenedisulfonyl, unsubstituted or substituted with C 1 -C 12 alkyl, , Diphenylenedisulfonyl or oxydiphenylenedisulfonyl; Or R ' 3 is C 2 -C 12 alkylenedisulfonyl;
    X is halogen;
    R 4 is hydrogen, phenyl, unsubstituted or phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR 5 R 6 , C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 1 -C 18 alkyl substituted with C 2 -C 6 alkanoyl; R 4 is blocked with one or more —O— and is unsubstituted, or is phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbon C 2 -C 18 alkyl substituted with aryl, NR 5 R 6 , C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) -sulfonyl and / or C 2 -C 6 alkanoyl; R 4 is unsubstituted or is phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR 5 R 6 , C 1 C 2 -C 18 alkanoyl substituted with —C 12 -alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 -C 6 alkanoyl; R 4 is unsubstituted or is phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR 5 R 6 , C 1 C 1 -C 18 alkylsulfonyl substituted with —C 12 -alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 -C 6 alkanoyl; Or R 4 is phenylsulfonyl or (4-methylphenyl) sulfonyl;
    R 5 and R 6 are each independently hydrogen or unsubstituted, OH, C 1 -C 4 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl , C 1 -C 18 alkyl substituted with phenylamino, phenylaminocarbonyl, C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methyl-phenyl) sulfonyl and / or C 1 -C 6 alkanoyl Or; R 5 and R 6 are blocked with one or more —O— and are unsubstituted or substituted with OH, C 1 -C 4 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthio C 2 -C 18 alkyl substituted with carbonyl, phenylamino, phenylaminocarbonyl, C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 1 -C 6 alkanoyl Or; R 5 and R 6 are unsubstituted or are phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, phenylamino, phenyl C 2 -C 18 alkanoyl substituted with aminocarbonyl, C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 -C 6 alkanoyl; R 5 and R 6 are unsubstituted or are phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, phenylamino, phenyl C 1 -C 18 alkylsulfonyl substituted with aminocarbonyl, C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 -C 6 alkanoyl; R 5 and R 6 are phenyl, benzoyl, phenylsulfonyl, (4-methylphenyl) sulfonyl, 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 blocked with -O- or -NR 4- ;
    R 7 is hydrogen, phenyl, unsubstituted or phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR 5 R 6 , C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 1 -C 18 alkyl substituted with C 2 -C 6 alkanoyl; R 7 is blocked with one or more —O— and is unsubstituted, or is phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbon N 2 , C 2 -C 18 alkyl substituted with NR 5 R 6 , C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 -C 6 alkanoyl; R 7 is unsubstituted or is phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR 5 R 6 , C 1 C 2 -C 18 alkanoyl substituted with —C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 -C 6 alkanoyl; R 7 is unsubstituted or is phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR 5 R 6 , C 1 C 1 -C 18 alkylsulfonyl substituted with —C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 -C 6 alkanoyl; Or R 7 is phenylsulfonyl or (4-methylphenyl) sulfonyl;
    R 8 , R 9 and R 10 are independently of each other unsubstituted or substituted C 1 -C 6 alkyl substituted with halogen; R 8 , R 9 and R 10 are unsubstituted or phenyl substituted with C 1 -C 4 alkyl or halogen; Or R 9 and R 10 together are 1,2-phenylene or C 2 -C 6 -alkylene unsubstituted or substituted with C 1 -C 4 alkyl or halogen.
    The compounds of the formulas (1), (2) and (3) are characterized in that they comprise at least two halogen atoms in one carbon atom after the oxymino group. Preferably the compound comprises three halogen atoms in one carbon atom after the oxymino group.
    C 1 -C 18 alkyl is straight or branched, for example C 1 -C 8- , C 1 -C 6 -or C 1 -C 4 -alkyl. For example methyl, ethyl, propyl, isopropyl, n-butyl, secondary-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, Non-yl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, preferably C 1 -C 4 alkyl such as methyl, iso-propyl or butyl.
    C 1 -C 8 alkyl, C 1 -C 6 alkyl and C 1 -C 4 alkyl are also straight or branched chains, for example, the carbon number is no more than the appropriate number as defined above. Of interest are, for example, C 1 -C 8- , in particular C 1 -C 6- , preferably C 1 -C 4 -alkyl, such as methyl or butyl. R 1 is, for example, C 2 -C 12- , C 4 -C 12- , C 8 -C 12- , C 4 -C 8 -alkyl Base to avoid the disclaimer for the compounds.
    An -O-, or by a block once or several times, for example, discontinuous once to five times by -O-, for example, block, once to three times or once or twice C 2 -C 12 alkyl. Thus, the structural units obtained are, for example, -O (CH 2 ) 2 OH, -O (CH 2 ) 2 OCH 3 , -O (CH 2 CH 2 O) 2- CH 2 CH 3 , -CH 2- O-CH 3 , -CH 2 CH 2 -O-CH 2 CH 3 ,-[CH 2 CH 2 O] y -CH 3 (where y is 1 to 5),-(CH 2 CH 2 O) 5 CH 2 CH 3 , —CH 2 —CH (CH 3 ) —O—CH 2 —CH 2 CH 3 or —CH 2 —CH (CH 3 ) —O—CH 2 —CH 3 .
    C 3 -C 30 cycloalkyl is a mono- or polycyclic cycloaliphatic ring, for example a mono-, non- or tricyclic cycloaliphatic ring, ie C 3 -C 20- , C 3 -C 18- , C 3 -C 12- , C 3 -C 10 cycloalkyl. Examples of monocyclic rings are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl, in particular cyclopentyl and cyclohexyl. Examples of polycyclic rings include perhydroanthrasyl, perhydropheniatril, perhydronaphthyl, perhydrofluorenyl, perhydrocrissenyl, 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] undecyl, bicyclo [4.3.3] dodecyl, Bicyclo [3.3.3] undecyl, bicyclo [4.3.1] decyl, bicyclo [4.2.1] nonyl, bicyclo [3.3.1] nonyl and bicyclo [3.2.1] octyl. Also "spiro" -cycloalkyl compounds are included in the definition C 3 -C 30 cycloalkyl in this context, ie spiro [5.2] octyl, spiro- [5.4] decyl, spiro [5.5] undecyl. Further examples of polycyclic cycloalkyl groups belonging to the respective definitions of the compounds of the present invention are listed in EP 878738 pages 11 and 12, in which to achieve "work" in compounds (1) to (46) Is combined. Those skilled in the art are well aware of this fact. In general, cycloalicyclic rings can form repeated structural units.
    C 2 -C 12 alkenyl radicals can be mono- or polyunsaturated, can be straight or branched, for example C 2 -C 8- , C 2 -C 6 -or C 2 -C 4 alkenyl to be. Examples include allyl, metalyl, vinyl, 1,1-dimethylallyl, 1-butenyl, 3-butenyl, 2-butenyl, 1,3-pentadienyl, 5-hexenyl or 7-octenyl, in particular There is allyl or vinyl.
    C 4 -C 8 cycloalkenyl may have one or more double bonds, for example C 4 -C 6 cycloalkenyl or C 6 -C 8 cycloalkenyl. Examples are cyclobutenyl, cyclopentenyl, cyclohexenyl or cyclooctenyl, in particular cyclopentenyl and cyclohexenyl, preferably cyclohexenyl.
    C 6 -C 12 bicycloalkenyl refers to a bicyclic alkenyl group which may have one or more double bonds, which may be located in the same ring but also in both rings. If several double bonds are present in the cycle, the double bonds can be conjugated or unconjugated, preferably the double bonds are conjugated. Examples include bicyclo [4.2.4] dodec-3,7-diene-5-yl, bicyclo [4.2.4] dodec-3-en-5-yl, bicyclo [4.2.4] dodec-4-ene -6-day, 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, examples of which are mentioned according to the following numbering.
    C 2 -C 12 alkylene is straight or branched chain, for example C 2 -C 8- , C 2 -C 6 -or C 2 -C 4 -alkylene. Examples are ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene and dodecylene. Preference is given to C 1 -C 8 alkylenes, in particular C 1 -C 6 -alkylene, preferably C 1 -C 4 alkylene, such as methylene or butylene. Thus, C 2 -C 12 alkylenedisulfonyl is an alkylene radical as indicated above which produces sulfonyl groups at both “yl” -residues. Examples include -SO 2- (CH 2 CH 2 ) z -SO 2- , where z is 1 to 6, that is, -SO 2 -CH 2 CH 2 -SO 2 -or -SO 2 -CH (CH 3 ) CH 2 -SO 2- .
    Phenylenedisulfonyl, diphenylenedisulfonyl and oxydiphenylenedisulfonyl also produce sulfonyl groups in the "one" residue. Thus, the structure obtained is , Yes, , or ; , Yes, ; , Yes, to be.
    Substituted phenyl has 1 to 5, for example 1 to 3, in particular 1 or 2 substituents on the phenyl ring. Substitution preferably occurs at the 4-, 3,4-, 3,5- or 3,4,5-position of the phenyl ring. The radical C 1 -C 18 alkyl in the group C 1 -C 18 alkylsulfonyl means straight or branched chain and has the meanings described above. The radicals C 3 -C 30 cycloalkyl in the group C 3 -C 30 cycloalkylsulfonyl have the meanings described above. Naphthyl, phenanthryl, heteroaryl and anthracyl are substituted by one or more radicals, which are for example mono- to 5-substituted, for example mono-, di- or tri-substituted, in particular mono- or bi- It is replaced.
    R 1 is phenyl substituted by OR 4 , NR 5 R 6 and / or SR 7 and the substituents OR 4 , NR 5 R 6 and SR 7 are substituted on the phenyl ring via the radicals R 4 , R 5 , R 6 or R 7 When forming a 5- or 6-membered ring with one carbon atom of another substituent or phenyl ring, for example, the following structural unit is obtained:
    , , or .
    As used herein, the term "heteroaryl" refers to a substituted or unsubstituted radical such as 3-thienyl, 2-thienyl, , , Wherein R 5 and R 6 are as defined above, thianthrenyl, isobenzofuranyl, xanthenyl, phenoxanyl, or (Wherein Y is S, O or NR 4 and R 4 is as defined above). Examples thereof include pyrazolyl, thiazolyl, oxazolyl, isothiazolyl or isoxazolyl. Also, for example, furyl, pyrrolyl, 1,2,4-thiazolyl, Or 5-membered ring heterocycles having fused aromatic groups, such as benzimidazolyl, benzothienyl, benzofuranyl, benzoxazolyl and benzothiazolyl.
    Other examples of "heteroaryl" include pyridyl, especially 3-pyridyl, Wherein R 4 is as defined above, pyrimidinyl, pyrazinyl, 1,3,5-triazinyl, 2,4-, 2,2- or 2,3-diazinyl, indolinyl, iso Indolyl, indolyl, indazolyl, furinyl, isoquinolyl, quinolyl, phenoxazinyl or phenazinyl. As used herein, the term "heteroaryl" also refers to radicals thioxanthyl, xanthyl, , (Wherein m is 0 or 1 and R 4 , R 5 and R 6 are as defined above), Or anthraquinonyl. Each heteroallyl may carry a substituent as indicated above or in claim 1. Camphoryl, 10-camphoryl, camphor-10-day, ie to be
    C 2 -C 6 alkanoyl is for example acetyl, propionyl, butanoyl or hexanoyl, in particular acetyl.
    C 1 -C 4 alkoxy is for example methoxy, ethoxy, propoxy and butoxy and alkyl radicals in alkoxy groups having two or more carbon atoms may also be branched.
    C 1 -C 4 alkylthios are, for example, methylthio, ethylthio, propylthio and butylthio, and the alkyl radicals in the alkylthio group having two or more carbon atoms may also be side chains.
    C 2 -C 6 alkoxycarbonyl is (C 1 -C 5 alkyl) -OC (O) —, wherein C 1 -C 5 alkyl has the appropriate number of carbon atoms as defined above. Examples are methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl or pentoxycarbonyl and alkyl radicals in alkoxy groups having two or more carbon atoms may also be branched.
    C 1 -C 10 haloalkyl and C 1 -C 4 haloalkyl, for example, as defined above, halogen, C 1 -C 10 - and C 1 -C 4 - one or a multiple-alkyl-substituted C 1 - C 10 -and C 1 -C 4 -alkyl. For example, there are one to three, or one or two halogen substituents in the alkyl radical. Examples are chloromethyl, trichloromethyl, trifluoromethyl or 2-bromopropyl, in particular trifluoromethyl or trichloromethyl. C 1 -C 10 fluoroalkyl is preferred.
    C 2 -C 6 haloalkanoyl is (C 1 -C 5 haloalkyl) -C (O)-, wherein C 1 -C 5 haloalkyl has up to the appropriate number of carbon atoms as defined above. Examples are chloroacetyl, trichloroacetyl, trifluoroacetyl, pentafluoropropionyl, perfluorooctanoyl or 2-bromopropionyl, in particular trifluoroacetyl or trichloroacetyl.
    Halobenzoyl is benzoyl mono- or polysubstituted with halogen and / or C 1 -C 4 haloalkyl, C 1 -C 4 -haloalkyl as defined above. Examples are pentafluorobenzoyl, trichlorobenzoyl, trifluoromethylbenzoyl, in particular pentafluorobenzoyl.
    Halogen is fluorine, chlorine, bromine or iodine, in particular chlorine or fluorine, preferably fluorine.
    Phenyl-C 1 -C 3 alkyl is, for example, benzyl, 2-phenylethyl, 3-fetylpropyl, α-methylbenzyl or α, α-dimethylbenzyl, in particular benzyl.
    Oxydiphenylene to be.
    When R 5 and R 6 together with the nitrogen atom to which they are attached form a 5-, 6- or 7-membered ring which can be interrupted by -O- or -NR 4- , for example, the following structure is obtained do:
    , , or .
    Definitions C 1 -C 18 alkylsulfonyl, phenyl-C 1 -C 3 alkylsulfonyl, camphorylsulfonyl, C 1 -C 10 haloalkylsulfonyl are sulfonyl groups (-SO 2- Corresponding C 1 -C 18 alkyl, phenyl-C 1 -C 3 alkyl, camphoryl and C 1 -C 10 haloalkyl. Thus, phenylsulfonyl, naphthylsulfonyl, anthracylsulfonyl and phenanthrylsulfonyl also refer to the corresponding radicals linked to sulfonyl groups. R 3 is for example C 2 -C 18- , C 4 -C 12- , C 6 -C 18- , C 4 -C 10 -alkylsulfonyl Base to avoid the disclaimer for the compounds.
    The group which has a -OC- bond or -O-Si-bond which is decomposed upon the action of an acid and is a substituent of the radical R 1 is a compound represented by Chemical Formula 1, Chemical Formula 2 or Chemical Formula 3, or Chemical Formula 1b, Chemical Formula 2b in alkaline developer after reaction with acid. Or an acid degradable group which increases the solubility of a compound of formula 3b, wherein formulas 1b, 2b and 3b are shown below. This effect is described, for example, in US 4883740.
    Examples of suitable groups as substituents on the radical R 1 are, for example, orthoesters, trityl and benzyl groups of carboxylic acids, tert-butyl esters, tert-butyl carbonates of phenols or silyl ethers of phenols, ie -OSi ( CH 3 ) 3 , , , or Wherein R 11 and R 12 independently of one another are hydrogen, C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl or phenyl-C 1 -C 3 alkyl, or R 11 and R 12 together represent C 2 − C 5 alkylene and R 13 is unsubstituted or halogen substituted C 1 -C 10 alkyl, unsubstituted or halogen substituted C 3 -C 8 cycloalkyl or phenyl-C 1 -C 3 -alkyl, or R 11 and R 12 together may not be C 2 -C 5 alkylene, and R 13 and R 12 together may be C 2 -C 5 alkylene which may be interrupted by —O— or —S-atom.
    In the claims, the term “and / or” or “or / and” refers not only to one of the defined substitutes (substituents) that may be present but also to all of the several defined substitutes (substituents), ie mixtures of different substitutes (substituents). Indicates.
    The term "at least" means one or more, for example one or two or three, preferably one or two.
    The present invention also relates to novel compounds of formula (Ib), (2b) or (3b).

    In the above formula,
    R ″ 1 is unsubstituted or one or more C 1 -C 12 alkyl, phenyl-C 1 -C 3 -alkyl, C 1 -C 4 haloalkyl, halogen, phenyl, OR 4 , NR 5 R 6 , SR 7 , Phenyl substituted with SOR 7 and / or SO 2 R 7 , and optionally the substituents OR 4 , SR 7 and NR 5 R 5 are further substituents on the phenyl ring via the radicals R 4 , R 5 , R 6 and / or R 7 Or together with one carbon atom of the phenyl ring form a 5- or 6-membered ring; R ″ 1 is unsubstituted or C 1 -C 6 alkyl, phenyl, OR 4 , NR 5 R 6 , SR 7 , SOR 7 And / or naphthyl, anthracyl or phenanthryl substituted by SO 2 R 7 and optionally the substituents OR 4 , SR 7 and NR 5 R 5 are via the radicals R 4 , R 5 , R 6 and / or R 7 Form a 5- or 6-membered ring with additional substituents on the phenyl ring or one carbon atom of the naphthyl, anthracyl or phenanthryl ring or one carbon atom of the naphthyl, anthracyl or phenanthryl ring; Or R ″ 1 is a heteroaryl radical unsubstituted or substituted with C 1 -C 6 alkyl, phenyl, OR 4 , NR 5 R 6 , SR 7 , SOR 7 and / or SO 2 R 7 , optionally substituted OR 4 , SR 7 and NR 5 R 6 may be substituted via a radical R 4 , R 5 , R 6 and / or R 7 together with a further substituent on the heteroaryl ring or with one carbon atom of the heteroaryl ring to form a 5- or 6-membered ring; Form;
    R ''' 1 is unsubstituted or substituted with C 1 -C 12 alkyl, phenylene, naphthylene, , Diphenylene or oxydiphenylene; Or R ''' 1 ego;
    A is -O-, -S-, -NR 4- , -O (CO)-, -S (CO)-, -NR 4 (CO)-, -SO-, -SO 2 -or -OSO 2- Is;
    A 1 is C 1 -C 12 alkylene or C 2 -C 12 alkylene blocked with one or more -O-;
    R ″ 3 is C 1 -C 16 alkylsulfonyl, phenyl-C 1 -C 3 alkylsulfonyl, camphorylsulfonyl, naphthylsulfonyl, trimethylphenylsulfonyl, or one or more C 2 -C 16 alkyl, C 1- Phenylsulfonyl substituted with C 4 alkoxy, C 1 -C 4 haloalkyl and / or halogen;
    R ' 3 is phenylenedisulfonyl, naphthylenedisulfonyl, unsubstituted or substituted with C 1 -C 12 alkyl, , Diphenylenedisulfonyl or oxydiphenylenedisulfonyl; Or R ' 3 is C 2 -C 12 alkylenedisulfonyl;
    R 4 is hydrogen, phenyl, unsubstituted or phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxy-carbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR 5 R 6 , C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 1 -C 12 alkyl substituted by C 2 -C 6 alkanoyl; R 4 is interrupted by one or more —O— and is unsubstituted or substituted with phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthio carbonyl, NR 5 R 6, C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 -C 6 alkanoyl substituted with a C 2 -C 12 alkyl, or by; R 4 is unsubstituted or is phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR 5 R 6 , C 1 -C 12- alkyl-sulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 a C 2 -C 12 alkanoyl which is substituted by -C 6 alkanoyl, or; R 4 is unsubstituted or is phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR 5 R 6 , C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 -C 6 alkynyl optionally substituted by a C 1 -C 12 alkanoyl or alkylsulfonyl; Or R 4 is phenylsulfonyl or (4-methylphenyl) sulfonyl;
    R 5 and R 6 are each independently hydrogen or unsubstituted, OH, C 1 -C 4 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl , phenylamino, phenyl-aminocarbonyl, C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methyl-phenyl) sulfonyl and / or C 1 -C 6 alkanoyl of C 1 -C 12 alkyl substituted with Or; R 5 and R 6 are interrupted by one or more —O—, unsubstituted, OH, C 1 -C 4 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenyl thiocarbonyl, phenylamino, phenyl-aminocarbonyl, C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 1 -C 6 alkanoyl substituted by a C 2 -C 12 alkyl; R 5 and R 6 are unsubstituted or phenyl, OH, C 1 -C 12 -alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, phenylamino, C 2 -C 12 alkanoyl substituted by phenylaminocarbonyl, C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) -sulfonyl and / or C 2 -C 6 alkanoyl; R 5 and R 6 are unsubstituted or are phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, phenylamino, phenyl Aminocarbonyl, C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) -sulfonyl and / or C 1 -C 12 alkylsulfonyl substituted by C 2 -C 6 alkanoyl; R 5 and R 6 are phenylsulfonyl or (4-methylphenyl) sulfonyl; R 5 and R 6 are phenyl, benzoyl, 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 optionally blocked with -O- or -NR 4- ;
    R 7 is hydrogen, phenyl, unsubstituted or phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR 5 R 6 , C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 1 -C 12 alkyl substituted with C 2 -C 6 alkanoyl; R 7 is blocked with one or more —O— and is unsubstituted, or is phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbon N 2 , C 2 -C 12 alkyl substituted with NR 5 R 6 , C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) -sulfonyl and / or C 2 -C 6 alkanoyl; R 7 is unsubstituted or is phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR 5 R 6 , C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 -C 6 alkynyl optionally substituted with a C 2 -C 12 alkanoyl or alkanoyl; R 7 is unsubstituted or is phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR 5 R 6 , C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 -C 6 alkynyl optionally substituted with a C 1 -C 12 alkanoyl or alkylsulfonyl; Or R 7 is phenylsulfonyl or (4-methylphenyl) sulfonyl; Provided that when R " 1 is 4-methylphenyl or 4-octylphenyl, R" 3 is not methanesulfonyl.
    Oxime derivatives of formulas (1), (1b), (2), (2), ( 3 ) and (3b) generally employ suitable free oximes (10) or (11), wherein R 3 and R ' 3 are H. Can be prepared by the method described in the literature by reacting with (15), (16) or (17), for example R 3 Cl or Cl-R ' 3 -Cl).
    In the above formula,
    R 1 , R 2 , R 3 , R ' 3 and X are as defined above. This reaction is generally carried out in the presence of a base such as tertiary amine (eg triethylamine) in an inert solvent such as, for example, toluene, tetrahydrofuran (THF) or dimethylformamide (DMF), or This is done by reacting the salt of oxime with the desired acid chloride. These methods are described, for example, in EP 48515. The sodium salt of oxime can be obtained, for example, by reacting the oxime in question with sodium alcoholate in dimethylformamide. Such reactions are well known to those skilled in the art and are carried out at temperatures of −15 to + 50 ° C., preferably 0 to 20 ° C.
    Oximes required as starting materials can be found in standard chemistry textbooks (J. March, Advanced Organic Chemistry, 4th Edition, Wiley Interscience, 1992) or in certain papers (SR Sandler & W. Karo, Organic functional group preparations, Vol. 3). , Academic Press) can be obtained by a variety of methods described. One of the most common methods is, for example, reacting ketones with hydroxylamine or salts thereof in polar solvents such as ethanol or aqueous ethanol. In this case, a base such as sodium acetate can be added to adjust the pH of the reaction mixture. The reaction rate is pH dependent and it is well known that base can be added continuously or during the reaction. Basic solvents such as pyridine can also be used as the base and / or solvent or cosolvent. This reaction temperature is generally the reflux temperature of the mixture, generally about 60 to 120 ° C. Another convenient synthesis of oximes is to nitrate "active" methylene groups with nitric acid or alkyl nitriles. See Organic Syntheses coll. Vol. Alkaline conditions as described in VI (J. Wiley & Sons, New York, 1988), pp 199 and 840, and Organic Synthesis coll. Vol V, pp 32 and 373, coll. Vol. III, All of the acidic conditions described in pp 191 and 513, coll. vol. II, pp. 202, 204 and 363) are suitable for the preparation of oximes used as starting materials for the compounds according to the invention. Nitric acid is generally produced from sodium nitrate. For example, the alkyl nitrile can be methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite and isoamyl nitrite.
    The described synthesis may form isomeric forms of the compounds of Formulas 1, 2 and 3 or Formulas 1b, 2b and 3b. Double bonds of oxymino groups can exist in both the syn (cis, Z) and anti (trans, E) forms or as a mixture of two geometric isomers. In the present invention, individual geometric isomers and mixtures of two geometric isomers can be used. Accordingly, the present invention relates to mixtures of isomeric forms of the compounds of the formulas (1), (2) and (3) or (1b), (2b) and (3b).
    Formulas 1, 2 and 3 of the individual geometric isomers (forms Z and E) and mixtures of the two geometric isomers or compounds of formulas 1b, 2b and 3b may be used, but the formulas of certain configurations (temporarily designated as Z-forms) It has been found that compounds of 1, 2 and 3 or formulas 1b, 2b and 3b are more thermally stable than compounds of other configuration (temporary designation as E-form). Therefore, preference is given to using compounds of the invention of the formulas 1, 2 and 3 or of formulas 1b, 2b and 3b which are more thermally stable isomers (temporarily designated as Z-forms).
    The synthesis of the oximes required as starting materials can form mixtures in isomeric form. Surprisingly, it has been found that mixtures of the isomeric forms of oximes required as starting materials are converted to a single isomeric form (temporary designation as Z-form) by treating with acid. Using a single isomer (Z-type) oxime as starting material gives the compounds of formulas 1, 2 and 3 or formulas 1b, 2b and 3b of a more thermally stable single isomer. Accordingly, the present invention also relates to the process of 1) converting a corresponding isomeric mixture of oximes into a single isomeric form of oxime by treatment with an acid and 2) reacting the oxime of the single isomeric type with the desired acid halide. A method for synthesizing thermally more stable isomers of 2 and 3 or compounds of formulas 1b, 2b and 3b.
    Therefore, the object of the present invention
    (1) treating an isomeric mixture of the corresponding free oxime compound (10) or (11), obtained by conventional methods, with an acid, and
    (2) an oxime ester compound of the formula (1), (2) or (3) according to claim 1 by reacting the single isomer free oxime compound thus prepared with the corresponding acid halide (15), (16) and (17), or A specific process for the preparation of thermally stable isomers of oxime ester compounds of 1b, 2b or 3b.
    10
    (11)
    R 3 Cl (15)
    R " 3 Cl (16)
    Cl-R ' 3 -Cl (17)
    In the chemicals,
    R 1 , R 2 , R 3 and R ' 3 , and X are as defined above,
    R ″ 3 is as defined below.
    The conversion reaction of the isomeric mixture of oximes to the desired single isomer is generally hydrochloric acid, sulfuric acid, acetic acid, trifluoroacetic acid or trifluoro in an inert solvent such as methylene chloride, ethyl acetate, toluene, tetrahydrofuran or dimethylformamide. It is carried out in the presence of an acid such as methanesulfonic acid. This reaction is generally carried out at temperatures ranging from -15 ° C to + 120 ° C, preferably 0 ° C to 80 ° C, more preferably 5 ° C to 40 ° C. Compounds are separated by methods known to those skilled in the art, ie distillation, crystallization, chromatographic methods. Examples of conventional methods for obtaining the oxime compound (10) or (11) as starting material are shown below.
    R 1 is hydrogen; Unsubstituted C 2 -C 12 alkyl; C 1 -C 12 alkyl substituted with C 3 -C 30 cycloalkyl; R 1 is C 2 -C 12 alkenyl, C 4 -C 8 cycloalkenyl, C 6 -C 12 bicycloalkenyl or camphoryl; R 1 is phenyl substituted with one or more radicals C 10 -C 12 -alkyl, C 1 -C 4 haloalkyl, chlorine, OR 4 , NR 5 R 6 , SR 7 and / or -S-phenyl, optionally substituted OR 4 , SR 7 and NR 5 R 6 form a 5- or 6-membered ring together with the further substituents on the phenyl ring or one carbon atom on the phenyl ring via the radicals R 4 , R 5 , R 6 and / or R 7 Form; R 1 is 2-naphthyl, anthracyl or phenanthryl unsubstituted or substituted with C 1 -C 6 alkyl, phenyl, OR 4 , NR 5 R 6 , SR 7 and / or -S-phenyl, optionally substituted OR 4 , SR 7 and NR 5 R 6 are further substituents on the naphthyl, anthracyl or phenanthryl ring or naphthyl, anthracyl or phenanthryl ring via the radicals R 4 , R 5, R 6 and / or R 7 Together with one or more carbon atoms of the phase form a 5- or 6-membered ring; Or R 1 is a heteroaryl radical which is unsubstituted or substituted by C 1 -C 6 alkyl, phenyl, OR 4 , NR 5 R 6 , SR 7 and / or —S-phenyl, optionally substituted OR 4 , SR 7 And NR 5 R 6 together with the further substituents on the heteroaryl ring or one carbon atom on the heteroaryl ring via the radicals R 4 , R 5 , R 6 and / or R 7 form a 5- or 6-membered ring or ; All radicals R 1 except hydrogen may be further substituted by a group having an —OC— bond or —O—Si—bond which decomposes upon the action of an acid;
    R 4 is phenyl, unsubstituted or phenyl, OH, C 1 -C 12 alkoxy, C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 -C 6 alkanoyl C 2 -C 12 alkyl substituted by; Or R 4 is interrupted by one or more —O— and is unsubstituted, or is phenyl, OH, C 1 -C 12 alkoxy, C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 -C 6 alkanoyl substituted with a C 2 -C 12 alkyl, or by;
    R 7 is unsubstituted or C 2 -C 12 alkyl substituted by OH and / or C 1 -C 4 alkoxy; Or R 7 is C 2 -C 12 alkyl which is interrupted by one or more —O—, unsubstituted or substituted by OH and / or C 1 -C 4 alkoxy;
    All other radicals are of interest to compounds of formulas 1b, 2b and 3b as described above.
    Base for a claim without the disclaimer, all defintions used in the disclaimer missing in the original definition of R 3 .
    R 3 is C 2 -C 18 alkylsulfonyl, C 1 -C 10 haloalkylsulfonyl, camphorylsulfonyl, phenyl-C 1 -C 3 alkylsulfonyl, C 3 -C 12 cycloalkylsulfonyl, naphthylsulfonyl , Anthracylsulfonyl or phenanthrylsulfonyl, wherein the radical C 3 -C 12 cycloalkylsulfonyl, phenyl-C 1 -C 3 alkylsulfonyl, phenylsulfonyl, naphthylsulfonyl, anthracylsulfonyl and phenanthrylsul The cycloalkyl, naphthyl, anthracyl and phenanthryl groups of the fonyl may be unsubstituted or substituted with one or more halogen, C 1 -C 4 haloalkyl, CN, NO 2 , C 1 -C 16 alkyl, phenyl, C 1 -C 4 Substituted by alkylthio, OR 4 , COOR 7 , C 1 -C 4 alkyl- (OC) O—, R 7 OSO 2 — and / or —NR 5 R 6 ; R 3 is at least one halogen, C 1 -C 4 haloalkyl, CN, NO 2 , C 2 -C 16 alkyl, phenyl, C 1 -C 4 alkylthio, OR 4 , COOR 7 , R 7 OSO 2 -and / Or phenyl substituted by -NR 5 R 6 ; Or R 3 is C 2 -C 6 haloalkanoyl or halobenzoyl;
    R 4 is phenyl, unsubstituted or phenyl, OH, C 1 -C 12 alkoxy, C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 -C 6 alkanoyl C 1 -C 12 alkyl substituted by; Or R 4 is interrupted by one or more —O— and is unsubstituted, or is phenyl, OH, C 1 -C 12 alkoxy, C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) -sulfonyl And / or C 2 -C 12 alkyl substituted by C 2 -C 6 alkanoyl;
    Also of interest are compounds of formulas 1b, 2b and 3b, wherein all other radicals are as defined above.
    R 1 is unsubstituted or one or more radicals C 1 -C 12 -alkyl, phenyl-C 1 -C 3 -alkyl, halogen, OR 4 , NR 5 R 6 , SR 7 , SOR 7 and / or SO 2 R 7 Is phenyl substituted with the substituent OR 4 optionally forming a 6-membered ring via the radical R 4 ; Or R 1 is naphthyl or thienyl;
    R ' 1 Is;
    A is -O- or -S-;
    A 1 is C 1 -C 12 alkylene;
    R 2 is halogen or C 1 -C 10 haloalkyl;
    R 3 is C 1 -C 18 alkylsulfonyl, camphorylsulfonyl, phenyl-C 1 -C 3 alkylsulfonyl, phenylsulfonyl or naphthylsulfonyl, wherein the phenyl group of the radical phenylsulfonyl is unsubstituted, Substituted by C 1 -C 16 alkyl or OR 4 ;
    R ' 3 is phenylenedisulfonyl;
    X is fluoro;
    R 4 is phenyl, C 1 -C 18 alkyl unsubstituted or substituted by C 2 -C 12 -alkoxycarbonyl; Or R 4 is C 2 -C 18 alkyl blocked with one or more —O— and substituted by phenyl;
    R 5 and R 6 are C 1 -C 18 alkyl;
    Of particular interest are compounds of formula 1, 1b, 2, 2b, 3 or 3b, wherein R 7 is phenyl or C 1 -C 18 alkyl.
    R 1 is phenyl unsubstituted or substituted by one or more radicals C 1 -C 12 alkyl, halogen, OR 4 or SR 7 ;
    R 2 is fluoro or C 1 -C 6 fluoroalkyl;
    R 3 is C 1 -C 12 alkylsulfonyl, camphor-10-ylsulfonyl, naphthylsulfonyl, phenylsulfonyl, wherein the phenyl group of this radical is unsubstituted or one or more C 1 -C 16 alkyl or Substituted by OR 4 ;
    X is fluorine;
    R 4 is C 1 -C 4 alkyl;
    R 7 is C 1 -C 4 alkyl;
    i) when R 1 is phenyl, 4-methylphenyl and (methylthio) phenyl, and R 2 and X together are fluorine, R 3 is not 4-methylphenylsulfonyl;
    2) when R 1 is 4-methylphenyl or 4-octylphenyl and R 2 and X are both fluorine, R 3 is not 4-methylsulfonyl;
    2i) when R 1 is phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl, trifluoromethyl or cyclohexyl and R 2 and X are both fluorine, R 3 is not phenylsulfonyl;
    vi) When R 1 is phenyl, R 2 is pentafluoroethyl and X is fluorine, compounds of formula 1, 1b, 2, 2b, 3 or 3b where R 3 is not phenylsulfonyl are preferred.
    2,2,2-trifluoro-1-phenyl-ethanone oxime-O-methylsulfonate; 2,2,2-trifluoro-1-phenyl-ethanone oxime-O- (10-camphorylsulfonate); 2,2,2-trifluoro-1-phenyl-ethanone oxime-O- (4-methoxyphenylsulfonate); 2,2,2-trifluoro-1-phenyl-ethanone oxime-O- (1-naphthylsulfonate); 2,2,2-trifluoro-1-phenyl-ethanone oxime-O- (2-naphthylsulfonate); 2,2,2-trifluoro-1-phenyl-ethanone oxime-O- (2,4,6-trimethylphenylsulfonate); 2,2,2-trifluoro-1- (4-methylphenyl) -ethanone oxime-O- (10-camphorylsulfonate; 2,2,2-trifluoro-1- (4-methylphenyl)- Ethanone oxime-O- (methylsulfonate); 2,2,2-trifluoro-1- (2-methylphenyl) -ethanone oxime-O- (10-camphorylsulfonate); 2,2,2 -Trifluoro-1- (2,4-dimethylphenyl) -ethanone oxime-O- (10-camphorylsulfonate); 2,2,2-trifluoro-1- (2,4-dimethylphenyl ) -Ethanone oxime-O- (1-naphthyl-sulfonate); 2,2,2-trifluoro-1- (2,4-dimethylphenyl) -ethanone oxime-O- (2-naphthyl Sulfonate); 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) -ethanone oxime-O- (10-camphorylsulfonate); 2,2,2-trifluoro Rho-1- (2,4,6-trimethylphenyl) -ethanone oxime-O- (1-naphthylsulfonate); 2,2,2-trifluoro-1- (2,4,6-tri Methylphenyl) -ethanone oxime-O- (2-naphthylsulfonate); 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime-O-methylsulfonate; 2, 2,2-trifluoro-1- (4- Methylthiophenyl) -ethanone oxime-O-methylsulfonate; 2,2,2-trifluoro-1- (3,4-dimethoxyphenyl) -ethanone oxime-O-methylsulfonate; 2,2 , 3,3,4,4,4-heptafluoro-1-phenyl-butanone oxime-O- (10-camphorylsulfonate); 2,2,2-trifluoro-1- (phenyl)- Ethanone oxime-O-methylsulfonate; 2,2,2-trifluoro-1- (phenyl) -ethanone oxime-O-10-camphorylsulfonate; 2,2,2-trifluoro-1 -(Phenyl) -ethanone oxime-O- (4-methoxyphenyl) -sulfonate; 2,2,2-trifluoro-1- (phenyl) -ethanone oxime-O- (1-naphthyl) Sulfonate; 2,2,2-trifluoro-1- (phenyl) -ethanone oxime-O- (2-naphthyl) sulfonate; 2,2,2-trifluoro-1- (phenyl)- Ethanone oxime-O- (2,4,6-trimethylphenyl) -sulfonate; 2,2,2-trifluoro-1- (4-methylphenyl) -ethanone oxime-O- (10-camphoryl) Sulfonate; 2,2,2-trifluoro-1- (4-methylphenyl) -ethanone oxime-O-methyl-sulfonate; 2,2,2-trifluoro-1- (2-methylphenyl)- on Oxime -O- (10- camphoryl) sulfonate; 2,2,2-trifluoro-1- (2,4-dimethylphenyl) -ethanone oxime-O- (1-naphthyl) sulfonate; 2,2,2-trifluoro-1- (2,4-dimethylphenyl) -ethanone oxime-O- (2-naphthyl) sulfonate; 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) -ethanone oxime-O- (10-camphoryl) sulfonate; 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) -ethanone oxime-O- (1-naphthyl) sulfonate; 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) -ethanone oxime-O- (2-naphthyl) -sulfonate; 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime-O-methylsulfonate; 2,2,2-trifluoro-1- (4-thiomethylphenyl) -ethanone oxime-O-methylsulfonate; 2,2,2-trifluoro-1- (3,4-dimethoxyphenyl) -ethanone oxime-O-methylsulfonate; 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime-O- (4-methylphenyl) sulfonate; 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime-O- (4-methoxyphenyl) sulfonate; 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime-O- (4-dodecylphenyl) sulfonate; 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime-O-octylsulfonate; 2,2,2-trifluoro-1- (4-thiomethylphenyl) -ethanone oxime-O- (4-methoxyphenyl) sulfonate; 2,2,2-trifluoro-1- (4-thiomethylphenyl) -ethanone oxime-O- (4-dodecyl-phenyl) sulfonate; 2,2,2-trifluoro-1- (4-thiomethylphenyl) -ethanone oxime-O-octylsulfonate; 2,2,2-trifluoro-1- (4-thiomethylphenyl) -ethanone oxime-O- (2-naphthyl) sulfonate; 2,2,2-trifluoro-1- (2-methylphenyl) -ethanone oxime-O-methylsulfonate; 2,2,2-trifluoro-1- (4-methylphenyl) -ethanone oxime-O-phenylsulfonate; 2,2,2-trifluoro-1- (4-chlorophenyl) -ethanone oxime-O-phenylsulfonate; 2,2,3,3,4,4,4-heptafluoro-1- (phenyl) -butanone oxime-O- (10-camphoryl) -sulfonate; 2,2,2-trifluoro-1-naphthyl-ethanone oxime-O-methylsulfonate ex 31; 2,2,2-trifluoro-2-naphthyl-ethanone oxime-O-methylsulfonate ex 31; 2,2,2-trifluoro-1- [4-benzylphenyl] -ethanone oxime-O-methylsulfonate ex 32; 2,2,2-trifluoro-1- [4- (phenyl-1,4-dioxa-but-1-yl) phenyl] -ethanone oxime-O-methylsulfonate ex 33; 2,2,2-trifluoro-1-naphthyl-ethanone oxime-O-propylsulfonate ex 34; 2,2,2-trifluoro-2-naphthyl-ethanone oxime-O-propylsulfonate; 2,2,2-trifluoro-1- [4-benzylphenyl] -ethanone oxime-O-propylsulfonate; 2,2,2-trifluoro-1- [4-methylsulfonylphenyl] -ethanone oxime-O-propyl-sulfonate ex 36 = plan 2; 1,3-bis [1- (4-phenoxyphenyl) -2,2,2-trifluoro ethanone oxime-O-sulfonyl] phenyl ex 37; ; ; 2,2,2-trifluoro-1- [4-methyl-sulfonyloxyphenyl] -ethanone oxime-O-propyl-sulfonate plan 3; 2,2,2-trifluoro-1- [4-methylcarbonyloxyphenyl] -ethanone oxime-O-propyl-sulfonate plan 1; 2,2,2-trifluoro-1- [6H, -7H-5,8-dioxonaphth-2-yl] -ethanone oxime-O-propyl-sulfonate plan 4; 2,2,2-trifluoro-1- [4-methoxycarbonylmethoxyphenyl] -ethanone oxime-O-propylsulfonate plan 5; 2,2,2-Trifluoro-1- [4- (methoxycarbonyl)-(4-amino-1-oxa-pent-1-yl) -phenyl] -ethanone oxime-O-propylsulfonate plan 6; 2,2,2-trifluoro-1- [3,5-dimethyl-4-ethoxyphenyl] -ethanone oxime-O-propylsulfonate plan 8; 2,2,2-trifluoro-1- [4-benzyloxyphenyl] -ethanone oxime-O-propylsulfonate plan 9; 2,2,2-trifluoro-1- [2-thiophenyl] -ethanone oxime-O-propylsulfonate plan 10 and 2,2,2-trifluoro-1- [1-dioxa-ti Ofen-2-yl)]-ethanone oxime-O-propyl-sulfonate plan 11 is particularly preferred. Ultimately, methylsulfonyl, methoxy, ethoxy or methylcarbonyl groups can also be substituted by other long chain alkylsulfonyl, alkoxy or alkylcarbonyl groups. In addition, the methyl or propyl group of the oxime-O-alkylsulfonate group can be easily substituted with other alkyl groups.
    The compound of formula 1, 2 or 3 can be used as photosensitive acid donor in photoresist. The resist system may be prepared by a development step after a system comprising a compound of Formula 1, 2 or 3 is investigated in a phase-wise manner.
    Chemically amplified photoresists are understood as resist compositions in which the radiation sensitive component provides a catalytic amount of acid that continuously catalyzes the chemical reaction of one or more acid-sensitive components of the resist. This introduces a difference in solubility between the irradiated and unirradiated areas of the resist. Due to the catalytic nature of this process, one acid molecule initiates the reaction at multiple sites so that the reaction diffuses through the reactive polymer matrix from one reaction site to the next site unless it is removed or destroyed by the second reaction. . Thus, low acid concentrations are sufficient to cause a high difference in solubility between exposed and unexposed areas in the resist. That is, only low concentrations of latent compounds are required. As a result, resists with high contrast and high transparency at the exposure wavelength in the optical phase can be formulated, which in turn produces a steep vertical image profile at high photosensitivity. As a result of this catalytic process, however, the latent catalyst is chemically and thermally very stable (unless irradiated) which in most cases requires an post-exposure baking step to initiate or complete the catalytic reaction causing the soluble difference. It is required that it not be produced during resist storage or processing. In addition, it is required that the solubility of the latent catalyst in the liquid resist formulation and the solid resist film should be excellent in order to avoid any particle formation which would hinder the application of these resists in the microelectronic manufacturing method.
    In contrast, positive resist materials that are not based on chemical amplification mechanisms must contain high concentrations of latent acid, since this is only the acid concentration resulting from the latent acid under exposure that contributes to the increased solubility of the exposed areas in the alkaline developer. Because. Since low acid concentrations only slightly affect the change in the dissolution rate of the resist and the reaction typically proceeds in the absence of post-exposure bake, the chemical and thermal stability of the latent acid is less required than in the case of chemically amplified positive resists. . The resist also requires higher exposure to produce an amount of acid sufficient to achieve sufficient solubility in alkaline developer in the exposed areas, and also relatively low optical clarity (due to the high concentration of latent acid required) and thus It is also disadvantageous due to the low resolution and the inclined image. Thus, resist compositions based on non-chemical amplification techniques have poor photosensitivity, resolution and image quality compared to chemically amplified resists.
    From the above, the latent acid chemical and thermal stability is essential for chemically amplified resists and can act in non-chemically amplified resists are different acid diffusion requirements, acid concentration requirements, and thermal and chemical stability. It is clear that the requirement is not necessarily applicable to chemically amplified resists.
    R 1 in the compounds of Formulas 1, 2 and 3 is phenyl unsubstituted or substituted by C 1 -C 6 alkyl, phenyl, OR 4 , SR 7 , -S-phenyl, halogen and / or NR 5 R 6 Optionally, substituents OR 4 and NR 5 R 6 together with additional substituents of the phenyl ring or together with one carbon atom of the phenyl ring form a 5- and 6-membered ring via the radicals R 4 , R 5 and / or R 6 The photoresist composition is preferable.
    Other interesting photoresist compositions are those in which the compounds of formulas (1), (2) and (3) R 3 is C 1 -C 18 alkylsulfonyl, phenyl-C 1 -C 3 alkylsulfonyl, camphorylsulfonyl, C 1 -C 10 Haloalkylsulfonyl, phenylsulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl, wherein the radical phenyl-C 1 -C 3 alkylsulfonyl, phenylsulfonyl, naphthylsulfonyl, anthracylsulfonyl and phenan The groups phenyl, naphthyl, anthracyl and phenanthryl of the triylsulfonyl are unsubstituted or one or more halogen, C 1 -C 4 haloalkyl, CN, NO 2 , C 1 -C 16 alkyl, phenyl, C 1 -C 4 alkylthio, OR 4 , COOR 7 , C 1 -C 4 alkyl-OCO—, R 7 OSO 2 — and / or —NR 5 R 6 .
    Preferred are chemically amplified photoresist compositions of the invention comprising compounds of formulas (1), (2) and (3), wherein X and R 2 are both fluorine. Such compounds are referred to as compounds of the formulas 1a, 2a and 3a.

    In the above formula,
    R 1 , R ' 1 , R 3 and R' 3 are as defined above.
    R 1 is unsubstituted phenyl, or phenyl substituted by one or more C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio or halogen; R 3 is C 1 -C 16 alkylsulfonyl, C 3 -C 30 cyanoalkylsulfonyl, phenyl-C 1 -C 3 alkylsulfonyl, camphorylsulfonyl, naphthylsulfonyl or phenylsulfonyl; Wherein said radical is unsubstituted or substituted by C 1 -C 12 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 alkylthio, NO 2 or halogen Particularly preferred are chemically amplified photoresist compositions comprising the compound of.
    In another preferred composition according to the invention the radical R 1 excluding hydrogen is substituted by a group having an -OC- bond or -O-Si- bond which decomposes upon the action of an acid.
    The resist solubility difference between the irradiated and unirradiated regions resulting from the acid-catalyzed reaction of the resist material during or after irradiation of the resist can be of two types depending on the additional components present in the resist. If the composition according to the invention comprises a component which increases the solubility of the composition in the developer after irradiation, the resist is positive. Accordingly, the present invention relates to chemically amplified positive photoresists.
    On the other hand, if the components in the formulation reduce the solubility of the composition after irradiation, the resist is negative. Accordingly, the present invention also relates to a chemically amplified negative photoresist.
    -In the unexposed areas-reduces the dissolution rate of the alkali soluble binder resin additionally present in the resist formulation and is essentially alkali-insoluble in the unexposed areas so that the resist film remains in the unexposed areas after development in the alkaline solution, Monomer or polymeric compounds which can be degraded in the presence of an acid or rearranged in such a way that their reaction products are soluble in alkaline developer are referred to as dissolution inhibitors.
    The present invention provides, in certain embodiments, at least one polymer having an acid-labile group and (b) at least one chemical formula that (a1) is decomposed in the presence of an acid to increase the solubility of the resist film in an aqueous alkaline developer solution in the exposed area. A chemically amplified positive developable alkaline photoresist composition comprising 1, 2 or 3 compounds.
    Further embodiments of the present invention comprise (a2) one or more monomer or oligomer dissolution inhibitors and one or more alkali-soluble polymers having one or more acid-labile groups, which decompose in the presence of an acid to increase solubility in an aqueous alkaline developer solution and ( b) A chemically amplified positive developable alkaline photoresist composition comprising at least one compound of formula (1), (2) or (3).
    Another specific embodiment of the present invention is (a1) at least one polymer having an acid labile group which is decomposed in the presence of an acid to increase solubility in alkaline developer; (a2) monomer or oligomer dissolution inhibitors having one or more acid-labile groups, which decompose in the presence of an acid to increase alkaline solubility in exposed areas; (a3) alkali-soluble monomers, oligomers, or polymeric compounds at concentrations that maintain the resist film in an unexposed region that is still essentially insoluble in alkaline developer; And (b) at least one compound of formula (1), (2) or (3), a chemically amplified positive alkaline-developable photoresist composition.
    Accordingly, the present invention relates to one or more polymers having acid-labile groups which decompose in the presence of (a1) acid to increase solubility in aqueous alkaline developer solution and / or (a2) in an aqueous alkaline developer solution decomposed in the presence of acid. At least one monomer or oligomer dissolution inhibitor having an acid-labile group which increases the solubility of the and / or (a3) at least one alkali-soluble monomer, oligomer or polymer compound; And (b) at least one compound of formula (1), (2) or (3) as a photosensitive acid donor.
    The composition may also further comprise component (b) other photosensitive acid donors and / or (c) other additives.
    Such chemically amplified positive resist systems are described, for example, in E. Reichmanis, F. M. Houlihan, O. Nalamasu, T. X. Neenan, Chem. Mater. 1991, 3, 394; Or 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 that decompose in the presence of an acid to produce aromatic hydroxy groups, carboxyl groups, keto groups and aldehyde groups and increase solubility in aqueous alkaline developer solutions are, for example, alkoxyalkyl ether groups, Tetrahydrofuranyl ether group, tetrahydropyranyl ether group, tert-alkyl ester group, trityl ether group, silyl ether group, alkyl carbonate group, for example tert-butyloxycarbonyloxy-, 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.
    A polymer having a functional group capable of being incorporated into the positive resist according to the present invention, which can be decomposed by the action of an acid to increase the solubility of the resist including the polymer in the alkaline developer, has a main chain and / or a side chain thereof, It may preferably have an acid-labile group in its side chain.
    Polymers having acid-labile groups suitable for use in the present invention may be prepared by polymer-like reactions which partially or completely convert alkaline soluble groups to respective acid-labile groups, or for example EP 254853, EP 878738. Already bound acid labile groups, as described in EP 87929, JP-A-2-25850, JP-A-3-223223 and JP-A-4-251259 Directly by (co) -polymerization of monomers having
    The polymers having acid-labile groups bound to the polymer backbone in the present invention are preferably silylethers, acetals, ketals which are completely decomposed, for example, at relatively low post-exposure baking temperatures (typically from room temperature to 110 ° C.) and Deblocking reaction in the presence of a polymer having an alkoxyalkylester group (so-called "low activation energy blocking group"), and, for example, tert-butylester group or tert-butyloxycarbonyl (TBOC) group, or acid Other ester groups containing a secondary or tertiary carbon atom adjacent to the oxygen atom of the ester bond that requires a higher baking temperature (typically> 110 ° C.) to complete the It is a polymer having. It is also possible to use hybrid systems in which both the high activation energy blocking group and the low activation energy blocking group are present in one polymer. In addition, polymer mixtures of polymers each using a different blocking group chemistry can be used in the photosensitive positive resist composition according to the invention.
    Preferred polymers having acid-labile groups are polymers and copolymers comprising the following distinct monomer types:
    1) monomers containing acid-labile groups that decompose in the presence of an acid to increase solubility in an aqueous alkaline developer solution and
    2) monomers and / or which do not contain acid-labile groups and do not contain groups that contribute to alkali solubility
    3) monomers that contribute to the aqueous alkali solubility of the polymer.
    Examples of monomers of type 1) are: non-cyclic or cyclic secondary and tert-alkyl (meth) acrylates, for example butyl acrylate including t-butyl acrylate, t-butyl Butyl methacrylate including methacrylate, 3-oxocyclohexyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, 2-methyl-adamantyl (meth) acrylate, cyclohexyl (meth) acrylic Laterate, norbornyl (meth) acrylate, (2-tetrahydropyranyl) oxynorbornyl alcohol acrylate, (2-tetrahydropyranyl) oxymethyltricyclododecanmethanol methacrylate, trimethylsilylmethyl ( Meth) acrylate, (2-tetrahydropyranyl) oxynorbornyl alcohol acrylate, (2-tetrahydropyranyl) oxymethyltricyclododecanmethanol methacrylate, trimethylsilylme (Meth) acrylate o- / m- / p- (3-oxocyclohexyloxy) styrene, o- / m- / p- (1-methyl-1-phenylethoxy) styrene, o- / m- / p-tetrahydropyranyloxystyrene, o- / m- / p-adamantyloxystyrene, o- / m- / p-cyclohexyloxystyrene, o- / m- / p-norbornyloxystyrene , Acyclic or cyclic alkoxycarbonylstyrene, for example o- / m- / p-butoxycarbonylstyrene, pt-butoxycarbonylstyrene, o- / m- / p- (3- Oxocyclohexyloxycarbonyl) styrene, o- / m- / p- (1-methyl-1-phenylethoxycarbonyl) styrene, o- / m- / p-tetrahydropyranyloxycarbonylstyrene, o -/ m- / p-adamantyloxycarbonylstyrene, o- / m- / p-cyclohexyloxycarbonylstyrene, o- / m- / p-norbornyloxycarbonylstyrene, non-cyclic Or cyclic alkoxycarbonyloxystyrenes such as o- / m- / p-butoxycarbonyloxystyrene, pt-butoxycarbonyloxystyrene, o- / m- / p- (3-oxo Cyclohex Oxycarbonyloxy) styrene, o- / m- / p- (1-methyl-1-phenylethoxycarbonyloxy) styrene, o- / m- / p-tetrahydropyranyloxycarbonyloxystyrene, o -/ m- / p-adamantyloxycarbonyloxystyrene, o- / m- / p-cyclohexyloxycarbonyloxystyrene, o- / m- / p-norbornyloxycarbonyloxystyrene, b -Cyclic or cyclic alkoxycarbonylalkoxystyrenes, for example o- / m- / p-butoxycarbonylmethoxystyrene, p-t-butoxycarbonylmethoxystyrene, o- / m- / p- (3-oxocyclohexyloxycarbonylmethoxy) styrene, o- / m- / p- (1-methyl-1-phenylethoxycarbonylmethoxy) styrene, o- / m- / p-tetrahydropyranyloxy Carbonylmethoxystyrene, o- / m- / p-adamantyloxycarbonylmethoxystyrene, o- / m- / p-cyclohexyloxycarbonylmethoxystyrene, o- / m- / p-norbornyloxy Carbonylmethoxystyrene, trimethylsiloxystyrene, dimethyl (butyl) siloxystyrene, unsaturated alkyl acetates, eg For example, isopropenyl acetate and derivatives thereof.
    Monomers of type 1) having a low activation energy acid-labile group are, for example, p- or m- (1-methoxy-1-methylethoxy) -styrene, p- or m- (1-methoxy -1-methylethoxy) -methylstyrene, 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- (1-methoxyethoxy) -methylstyrene, 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-methylethoxy) styrene, p- or m- (1-n-propoxy-1-methylethoxy)- Methylstyrene, p- or m- (1-n-propoxyethoxy) styrene, p- or m- (1-n- Propoxyoxy) -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-methyl Propoxy) styrene, p- or m- (1-isopropoxy-1-methylpropoxy) -methylstyrene, p- or m- (1-isopropoxypropoxy) styrene, p- or m- (1 Isopropoxypropoxy) -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- (l-tert-butoxy-1-methylethoxy) styrene, p- or m- (1-n- Pentoxy-1-methylethoxy) styrene, p- or m- (1-isoamyloxy-1-methylethoxy) styrene, p- or m- (1-n-hexyloxy-1-methylethoxy Styrene, p- or m- (1-cyclohexyloxy-1-methyl Styrene, p- or m- (1-trimethylsilyloxy-1-methylethoxy) styrene, p- or m- (1-trimethylsilyloxy-1-methylethoxy) -methylstyrene, p- or m -(1-benzyloxy-1-methylethoxy) styrene, p- or m- (1-benzyloxy-1-methylethoxy) -methylstyrene, p- or m- (1-methoxy-1-methyl Ethoxy) styrene, p- or m- (1-methoxy-1-methylethoxy) -methylstyrene, p- or m- (1-trimethylsilyloxy-1-methylethoxy) styrene, p- or m -(1-trimethylsilyloxy-1-methylethoxy) -methylstyrene. Other examples of polymers having alkoxyalkyl ester acid labile groups are described in US Pat. No. 5,532,616 and EP 829766. Examples of polymers having acetal blocking groups are described in US Pat. No. 5,702,099, EP, 780,732, US, 5627006, US, 5,555,76, US, 5,589,71, US, 546,8589, EP, 704,762, EP, 762,206. 342498, EP 553737, and 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.
    For polymers having acetal groups as acid-labile groups, see, for example, H.-T. Schacht, P. Falcigno, N. Muenzel, R. Schultz and A. Medina, ACS Symp. Ser. 706, Micro- and Nanopatterning 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, may be introduced acid-labile crosslinks. Such crosslinked systems are preferred in view of the heat resistance of the resist pattern.
    Monomers having a high activation energy acid-labile group are, for example, p-tert-butoxycarbonyloxystyrene, tert-butyl-acrylate, tert-butyl-methacrylate, 2-methyl-2 Adamantyl-methacrylate, isobornyl-methacrylate.
    Examples of comonomers according to type 2) are as follows: aromatic vinyl monomers such as styrene, α-methylstyrene, acetoxystyrene, α-methylnaphthylene, acenaphthylene, vinyl alicyclic compounds, for example For example, vinyl norbornane, vinyl adamantane, vinyl cyclohexane, alkyl (meth) acrylates such as methyl methacrylate, acrylonitrile, vinylcyclohexane, vinylcyclohexanol and maleic anhydride.
    Examples of comonomers according to type 3) are as follows: vinyl aromatic compounds such as hydroxystyrene, acrylic acid compounds such as methacrylic acid, ethylcarbonyloxstyrene and derivatives thereof. These polymers are described, for example, in US 5827634, US5625020, US 5492793, US 5372912, EP 660187, US 5679495, EP 813113 and EP 831369. Further examples are crotonic acid, isocrontonic acid, 3-butene acid, acrylic acid, 4-pentenoic acid, propiolic acid, 2-butynic 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 can vary widely and depend on the alkali solubility of other comonomers and deprotected polymers. Typically, the content of monomers having acid-labile groups in the polymer is 5 to 60 mol%. If the content is too low, very low development rates and residuals of the resist in the exposed areas occur. If the content of the acid-labile monomer is too high, the resist pattern becomes unclear (eroded) after development and the three features are no longer resolved and / or the adhesion to the substrate during resist development is loose. Preferably the copolymer having an acid-labile group is from about 3'000 to about 200'000, more preferably from about 5'000 to about 50 'with a molecular weight distribution of about 3 or less, more preferably about 2 or less. Has an M w of 000. Non-phenolic polymers such as alkyl acrylates such as t-butyl acrylate or t-butyl-methacrylate and vinyl alicyclic compounds such as vinyl norbornanyl or vinyl cyclohexanol compounds are also free radicals. It may be prepared by polymerization or other known process, and suitably has an M w of about 8'000 to about 50'000 and a molecular weight distribution of about 3 or less. Copolymers other than these may be suitably added in an amount suitable for 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 can be used. For example, polymers having acid-labile groups that decompose very easily, such as acetal groups or tetrahydropyranyloxy- groups, and less readily decomposing acid-decomposable groups, such as tertiary Mixtures of polymers having alkyl ester groups can be used. In addition, acid decomposable groups of different sizes may be prepared by different acid degradable groups such as tert-butylester groups and 2-methyl-adamantyl groups or 1-ethoxy-ethoxy groups and tetrahydropyranyloxy It can combine by mixing 2 or more types of polymers which have a group. Mixtures of non-crosslinked resins and crosslinked resins may also be used. The amount of the polymer in the present invention is preferably 30 to 99% by weight, more preferably 50 to 98% by weight, based on the total amount of all solid components. Alkali-soluble resins or monomeric or oligomeric compounds that do not have acid-labile groups can also be incorporated into the compositions to control alkali solubility. Examples of polymer mixtures with polymers having different acid-labile groups are described in EP 780732, EP 6679951 and US 5817444.
    Preferably, monomer and oligomer dissolution inhibitor (a2) are used in the present invention. Monomer or oligomer dissolution inhibitors having acid-labile groups for use in the present invention are compounds having at least one acid-labile group in the molecular structure which degrade in the presence of acid to increase solubility in aqueous alkaline developer solutions. Examples include 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 group, vinyl carbamate group, tertiary alkyl carbamate group, trityl amino group, cumyl ester group, acetal group, ketal group, tetrahydropyranyl ester group, tetrafuranyl ester group, tertiary alkyl ether group, 3 Higher alkyl ester groups and the like. The molecular weight of the acid-degradable dissolution inhibiting compound for use in the present invention is 3'000 or less, preferably 100 to 3'000, more preferably 200 to 2'500.
    Examples of monomers and oligomer dissolution inhibitors having acid-labile groups are described in EP 0831369 as compounds (I) to (XVI). Dissolution inhibitors with other suitable acid-labile groups are described in US Pat. No. 5,367, 52, US Pat. No. 50,554, US 5015554, JP-A-1- 289946, JP-A-1-289947, JP-A-. 2- head 2560, JP-A-3- head 128959, JP-A-3- head 158855, JP-A-3- head 179353, JP-A-3- head 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, JP-A-3-279958, JP-A-3-279959, JP-A-4-1650, JP-A-4-1651, JP-A- No. 11260, JP-A-4-No. 12258, JP-A-4- No. 123567, JP-A-1- No. 289946, JP-A-3- No. 128959, JP-A-3- 158855, JP-A-3-179353, JP-A-3-1991351, JP-A-3-200251, JP-A-3-200252, JP-A-3- 200253, JP-A-3-200254, JP-A-3-200255, JP-A-3-259149, JP-A-3-279958, JP-A-3- No. 279959, JP-A-4-No. 1650, JP-A-4-No. 1651, JP-A-No. 11260, JP-A-4- No. 12566, JP-A-4- No. 12357 And Japanese Patent Application Nos. 3-332332, 3-230230, 3-320438, 4-254157, 4-52732 , 4-103103, 4-104542, 4-107885, 4-107107, 4-152195, 4-254157, 4-103215, 4-104542, 4 -107885, 4- 107885, 4-107107 and 4-152195.
    The compositions also contain polymeric dissolution inhibitors, for example together with alkaline soluble polymers or with polymers containing acid-labile groups that increase the solubility of resist films in the developer after exposure, or with both polymers of this type. , Polyacetals as described in US Pat. No. 5,533,433 or poly-N, O-acetals as described, for example, in US Pat. No. 5498506.
    When dissolution inhibitors having acid-labile groups are used in the present invention with oxime derivatives of formulas (1), (2) or (3), alkali-soluble polymers and / or polymers having acid-labile groups, the amount of dissolution inhibitor is determined by the amount of all solids in the photosensitive composition. 3 to 55% by weight, preferably 5 to 45% by weight, most preferably 10 to 35% by weight, based on the total amount of components.
    Polymers (a3) which are soluble in aqueous alkali solutions are preferably used in the present invention. Examples of these polymers include novolak resins, hydrogenated novolak resins, acetone-pyrogallol resins, poly (o-hydroxystyrene), poly (m-hydroxystyrene), poly (p-hydroxystyrene), hydrogenated poly (Hydroxystyrene), halogen- or alkyl-substituted poly (hydroxystyrene), hydroxystyrene / N-substituted maleimide copolymers, o / p- and m / p-hydroxystyrene copolymers, partially o-alkylated poly (hydroxystyrene) [e.g. o-methylated, o- (1-methoxy) ethylated, o- (1-ethoxy) ethylated with 5-30 mol% substitution of hydroxyl groups , o-2-tetrahydropyranylated and o- (t-butoxycarbonyl) methylated poly (hydroxystyrene)], o-acetylated poly (hydroxystyrene) [e.g., the degree of substitution of hydroxyl groups is 5 To 30 mol% o-acetylated and o- (t-butoxy) carbonylated poly (hydroxystyrene)], styrene / maleic anhydride copolymer, styrene / ha And a de-hydroxystyrene copolymer, α- methyl styrene / hydroxystyrene copolymers, carboxylated methacrylic resins, and derivatives thereof. Poly (meth) acrylic acid [eg poly (acrylic acid)], (meth) acrylic acid / (meth) acrylate copolymer [eg acrylic acid / methyl acrylate copolymer, methacrylic acid / methyl methacrylate copolymer or methacrylic Acid / methyl methacrylate / t-butyl methacrylate copolymer], (meth) acrylic acid / alkene copolymer [e.g. acrylic acid / ethylene copolymer], (meth) acrylic acid / (meth) acrylamide copolymer [e.g. Acrylic acid / acrylamide copolymer], (meth) acrylic acid / vinyl chloride copolymer [e.g. acrylic acid / vinyl chloride copolymer], (meth) acrylic acid / vinyl acetate copolymer [e.g. acrylic acid / vinyl acetate copolymer], maleic acid / Vinyl ether copolymers [e.g. maleic acid / methyl vinyl ether copolymer], maleic acid mono esters / methyl vinyl ester copolymer [e.g. maleic acid mono methyl ester / methyl vinyl ether copolymer], Leic acid / (meth) atrylic acid copolymers [eg maleic acid / acrylic acid copolymer or maleic acid / methacrylic acid copolymer], maleic acid / (meth) acrylate copolymers [eg maleic acid / methyl acrylate copolymer ], Maleic acid / vinyl chloride copolymers, maleic acid / butyl acetate copolymers and maleic acid / alkyl copolymers such as maleic acid / ethylene copolymers and maleic acid / 1-chloropropene copolymers are further suitable. . However, alkali-soluble polymers for use in the present invention should not be construed as being limited to these examples. Particularly preferred alkali-soluble polymers (a3) are novolak resins, poly (o-hydroxystyrene), poly (m-hydroxystyrene), poly (p-hydroxystyrene), for example p-vinylcyclohexane All, alkyl-substituted poly (hydroxystyrene), copolymers of the respective hydroxystyrene monomers with partially o- or m-alkylated and o- or m-acylated poly (hydroxystyrene), styrene / Hydroxystyrene copolymer, and α-methylstyrene / hydroxystyrene copolymer. Novolak resins are obtained by addition-condensation under an acid catalyst with at least one provided monomer and at least one aldehyde as main component.
    Examples of monomers useful for the preparation of alkaline soluble resins are hydroxylated aromatic compounds such as phenols, cresols, ie m-cresol, p-cresol and o-cresol, xylenol, for example 2,5 -Xylenol, 3,5-xylenol, 3,4-xylenol and 2,3-xylenol, alkoxyphenols such as p-methoxyphenol, m-methoxyphenol, 3, 5-dimethoxyphenol, 2-methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol and p-butoxy Phenols, dialkylphenols such as 2-methyl-4-isopropylphenol, and m-chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorci Other hydroxylated aromatics including knol and naphthol. These compounds may be used alone or in admixture of two or more thereof. Main monomers for novolak resins should not be construed as limited to the above examples. Examples of aldehydes for polycondensation with phenolic compounds to obtain novolac include formaldehyde, p-formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropionaldehyde, β-phenylpropionaldehyde, o -Hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde Benzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural, chloroacetaldehyde, and acetals derived therefrom such as chloroacetaldehyde diethyl acetal. Of these, formaldehyde is preferred. The aldehydes may be used alone or in combination of two or more thereof. Examples of acid catalysts include hydrochloric acid, sulfuric acid, formic acid, acetic acid and oxalic acid.
    The weight-average molecular weight of the novolak resin thus obtained is suitably 1'000 to 30'000. If its weight-average molecular weight is lower than 1'000, the film reduction in the unexposed areas during development is likely to be large. If its weight-average molecular weight exceeds 50'000, the development rate is very low. The molecular weight of the particularly preferable range of novolak resin is 2'000-20'000. Alkali-soluble polymers other than novolac resins, poly (hydroxystyrene) and derivatives and copolymers thereof, which are presented above, are each 2'000 or more, preferably 4'000 to 200'000, more preferably 5'000 To a weight-average molecular weight of from 50'000. In terms of obtaining a polymer having improved heat resistance, its weight-average molecular weight is preferably at least 5'000. By weight-average molecular weight in the context of the present invention is meant measured by gel permeation chromatography and calibrated with polystyrene standards.
    In the present invention, the alkali-soluble polymer can be used as a mixture of two or more thereof. When using a mixture of an alkali-soluble polymer and a polymer having a group decomposed by the action of an acid to increase the solubility in the alkaline developer, the amount of the alkali-soluble polymer added is based on the total amount of the photosensitive composition (excluding the solvent), Preferably it is 80 weight% or less, More preferably, it is 60 weight% or less, Most preferably, it is 40 weight% or less. An amount exceeding 80% by weight is undesirable because the thickness of the resist pattern is significantly reduced, leading to poor images and low resolution. When the alkali-soluble polymer is used together with the dissolution inhibitor in the absence of a polymer having a group which is decomposed by the action of an acid to increase the solubility in the alkaline developer, the amount of the alkali-soluble polymer is preferably 40 to 90% by weight, more It is preferably 50 to 85% by weight, most preferably 60 to 80% by weight. If the amount thereof is less than 40% by weight, undesirable results such as reduced photosensitivity occur. On the other hand, if it exceeds 90% by weight, the film thickness of the resist pattern is considerably reduced, leading to poor resolution and image reproducibility.
    The content of the oxime derivative (component (b)) of the formula (1), (2) or (3) in the positive resist according to the invention is preferably 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 act on the principle of removal from the polymer of the protecting group generally results in a positive resist. Positive resists are preferred over negative resists in many applications, especially because of their higher resolution. However, it is also of interest to create a negative phase using the positive resist mechanism, in order to combine the high resolution benefits of the positive resist with the properties of the negative resist. This can be achieved, for example, by introducing so-called image-reversal as described in EP 361906. For this purpose, the acid produced is subjected to the phase-modal neutralization of the phase-irradiated resist material prior to the development step, for example by gas base. Next, a second irradiation over the whole area, and thermal post-treatment are carried out, and then the negative phase is developed in a conventional manner.
    Characteristically, the photosensitive component that produces the negative resist will crosslink with itself and / or with components in one or more additional compositions, especially when catalyzed by an acid (e.g., an acid formed during irradiation of a compound of Formula 1, 2 or 3). Compound. Compounds of this type are, for example, known acid-curable resins such as acrylic acid, poly-esters, alkyds, melamines, ureas, 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 component is generally at a concentration of from 2 to 40% by weight, preferably from 5 to 30% by weight, based on the total solids content in the negative resist composition.
    As such, the invention provides, in certain embodiments, as (a4) an alkali-soluble resin as a binder, (a5) a component which alone and / or crosslinks with a binder when catalyzed by an acid, and (b) as a photosensitive acid donor Chemically amplified negative, alkali-developable photoresists comprising oxime derivatives of Formula 1, 2 or 3; The composition may also comprise (b) other photosensitive acid donors and / or (c) other additive components.
    Particularly preferred as acid-curable resins (a5) are amino resins, for example non-etherized or etherified melamine, urea, guanidine or biuret resins, in particular methylated melamine resins or butylated melamine resins, corresponding glycolurils and urones. Do. In this context, “resin” generally means both oligomers, conventional industrial mixtures that also include pure high purity compounds. N-hexa (methoxymethyl) melamine and tetramethoxymethyl gluconyl and N, N'-dimethoxymethyluron are the most preferred acid-curable resins.
    Generally, the concentration of the compound of formula 1, 2 or 3 in the negative resist is from 0.1 to 30% by weight, preferably up to 20% by weight, based on the total solids content in the composition. 1-15 weight% is especially preferable.
    If desired, the negative composition may comprise a film-forming polymeric binder (a4). The binder is preferably an alkali-soluble phenolic resin. For example, novolacs derived from aldehydes such as acetaldehyde or furfuraldehyde, especially formaldehyde, and phenols such as unsubstituted phenols, mono- or di-chloro substituted phenols, for example For example, p-chlorophenol, phenol mono- or di-substituted with C 1 -C 9 alkyl, for example o-, m- or p-cresol, various xylenols, p-tert-butylphenol, p- Nonylphenol, p-phenylphenol, resorcinol, bis (4-hydroxyphenyl) methane or 2,2-bis (4-hydroxyphenyl) propane are very suitable for this purpose. In addition, homo- and copolymers based on ethylenically unsaturated phenols, for example solely of vinyl- and 1-propenyl-substituted phenyls such as p-vinylphenol or p- (1-propenyl) phenol Polymers or copolymers of the phenols with one or more ethylenically unsubstituted materials, such as styrene, are suitable. The amount of binder should generally be 30 to 95% by weight, preferably 40 to 80% by weight.
    Particularly preferred negative resist compositions comprise 0.5 to 15% by weight of an oxime derivative [component (b)] of formula 1, 2 or 3, based on the percent solids content of the composition, phenolic resin [component (a4)] as a binder, For example, 40 to 99% by weight of one of the above, and 0.5 to 30% by weight of the melamine resin (component (a5)) as a crosslinking agent. Using novolac or in particular polyvinyl phenol as binder, a negative resist with particularly good properties is obtained.
    Oxime derivatives can also be used in photoresist systems as photochemically activated acid generators for acid-catalyzed crosslinking of poly (glycidyl) methacrylates, for example. Such crosslinking reactions are described, for example, in Chae et al., In Pollimo 1993, 17 (3), 292.
    Positive and negative resist compositions may contain additional photosensitive acid donor components (b1), additional additives (c), other photoinitiators (d) and / or sensitizers (e) in addition to the photosensitive acid donor compounds of formula (1), (2) or (3). It may include. Accordingly, the object of the present invention is also additional to components (a) and (b), or components (a1), (a2), (a3) and (b), or components (a4), (a5) and (b) Chemically amplified resist composition as described above, comprising additive (c), additional photosensitive acid donor component (b1), other photoinitiator (d), and / or sensitizer (e).
    Oxime derivatives of the present invention in positive and negative resists also contain other, known photolatonic acids (b1) such as onium salts, 6-nitrobenzylsulfonate, bis-sulfonyl diazomethane compounds, cyano group- It can be used together with the containing oxime sulfonate compound and the like. Examples of photocatalytic acids known for chemically amplified resists include US Pat. No. 5,397,642, US Pat. No. 5,800,964, EP Pat. No. 704762, US Pat. No. 5,585,895, US Pat. No. 5,589,71, US Pat. And EP 795786. When a mixture of photolatonic acids is used in the resist composition according to the invention, the weight ratio of the oxime derivatives of formula 1, 2 or 3 to the other photolatonic acids (b1) in the mixture is preferably 1:99 to 99: 1. .
    Examples of suitable photolatonic acids for use in admixture with the compounds of Formulas 1, 2 and 3 are as follows:
    (1) Onium salt compounds, such as iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts. Diphenyl iodonium triflate, diphenyl iodonium pyrenesulfonate, diphenyl iodonium dodecylbenzenesulfonate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, diphenyl iodo Hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, (hydroxyphenyl) benzylmethylsulfonium toluenesulfonate, and the like are preferable. Particular preference is given to triphenylsulfonium triflate and diphenyliodonium hexafluoroantimonate.
    (2) halogen-containing compounds such as haloalkyl group-containing heterocyclic compounds, haloalkyl group-containing hydrocarbon compounds and the like. (Trichloromethyl) -s-triazine derivatives such as phenyl-bis (trichloromethyl) -s-triazine, methoxyphenyl-bis (trichloromethyl) -s-triazine, naphthyl-bis (Trichloromethyl) -s-triazine and the like; 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane and the like are preferable.
    (3) sulfone compounds such as β-ketosulfone, β-sulfonylsulfone and α-diazo derivatives thereof and the like. Phenyl acylphenyl sulfone, mesityl penacyl sulfone, bis (phenyl sulfonyl) methane, and bis (phenyl sulfonyl) diazomethane are preferable.
    (4) sulfonate compounds such as alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, imino sulfonates, imido sulfonides and the like. Imidosulfonate compounds such as N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy ) Naphthylimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) -bicyclo [2,2,1] -hept-5-ene- 2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo- [2,2,1] -hept-5-ene-2,3-dicarboximide, N- (Trifluoromethylsulfonyloxy) -7-oxabicyclo- [2,2,1] -hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy)- Bicyclo- [2,2,1] -heptane-5,6-oxy-2,3-dicarboximide, N- (campanylsulfonyloxy) succinimide, N- (campanylsulfonyloxy) phthalimide , N- (campanylsulfonyloxy) naphthylimide, N- (campanylsulfonyloxy) diphenylmaleimide, N- (campanylsulfonyloxy) bicyclo- [2,2,1]- T-5-en-2,3-dicarboximide, N- (campanylsulfonyloxy) -7-oxabicyclo- [2,2,1] -hept-5-ene-2,3-dicarboximide , N- (campanylsulfonyloxy) -7-oxabicyclo- [2,2,1] hept-5-ene-2,3-dicarboximide, N- (campanylsulfonyloxy) -bicyclo- [ 2.2.1] -heptane-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-methylphenyl Sulfonyloxy) -bicyclo- [2,2,1] -hept-5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo- [2, 2,1] -hept-5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) -bicyclo- [2,2,1] -heptane-5,6-oxy-2 , 3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (2-trifluoro Methylphenylsulfonyloxy) naphthylimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) -bicyclo- [2,2, 1] -hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo- [2,2,1] -hept-5-ene -2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) -bicyclo- [2,2,1] -heptane-5,6-oxy-2,3-dicarboximide and the like This is preferable. Other suitable sulfonate compounds are preferably, for example, benzoin tosylate, pyrogallol tristriplate, pyrogallolomethanesulfonic acid triester, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, α- (4-toluene-sulfonyloxyimino) -benzyl cyanide, α- (4-toluene-sulfonyloxyimino) -4-methoxybenzyl cyanide, α- (4-toluene-sulfonyloxyimino) 2-thienylmethyl cyanide, α- (methanesulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (butylsulfonyloxyimino) -1-cyclopentenylacetonitrile, (4-methylsul Ponyyloxyimino-cyclohexa-2,5-dienylidene) -phenyl-acetonitrile, (5-methylsulfonyloxyimino-5H-thiophen-2-ylidene) -phenyl-acetonitrile, (5-methyl Sulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) -acetonitrile, (5-methylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-chloro Phenyl) acetonitrile and the like. In the irradiation sensitive resin composition of the present invention, particularly preferred sulfonate compounds are pyrogallol methanesulfonic acid triester, N- (trifluoromethylsulfonyloxy) bicyclo- [2,2,1] -hept-5-ene -2,3-dicarboximide, N- (campanylsulfonyloxy) naphthylimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) -Bicyclo- [2,2,1] -hept-5-ene-2,3-dicarboximide, N- (campanylsulfonyloxy) naphthylimide, N- (2-trifluoromethylphenylsulfonyl Oxy) phthalimide and the like.
    (5) Quinonediazide compounds, for example 1,2-quinonediazidesulfonic acid ester compounds of polyhydroxy compounds. 1,2-quinonediazidesulfonyl groups, for example 1,2-benzoquinonediazide-4-sulfonyl groups, 1,2-naphthoquinonediazide-4-sulfonyl groups, 1,2- Preferred are compounds having a naphthoquinone diazide-5-sulfonyl group, a 1,2-naphthoquinone diazide-6-sulfonyl group and the like. Particular preference is given to compounds having 1,2-naphthoquinonediazide-4-sulfonyl groups or 1,2-naphthoquinonediazide-5-sulfonyl groups. (Poly) hydroxyphenyl aryl ketones such as 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzo Phenone, 2,2 ', 3,4-tetrahydroxybenzophenone, 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'-hexa 1,2-quinonediazidesulfonic acid esters such as hydroxybenzophenone, 2,3 ', 4,4', 5 ', 6-hexahydroxybenzophenone; Bis-[(poly) hydroxyphenyl] alkanes such as bis (4-hydroxyphenyl) ethane, bis (2,4-dihydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl 1,2-quinonediazidesulfonic acid esters, such as propane, 2,2-bis (2,4-dihydroxyphenyl) propane, and 2,2-bis (2,3,4-trihydroxyphenyl) propane ; (Poly) hydroxyphenylalkanes such as 4,4'-dihydroxytriphenylmethane, 4,4 ', 4 "-trihydroxytriphenylmethane, 4,4', 5,5'-tetra Methyl-2,2 ', 2 "-trihydroxyphenylmethane, 2,2,5,5'-tetramethyl-4,4'4" -trihydroxytriphenylmethane, 1,1,1-tris ( 4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -1- (4- [1- (hydroxy 1,2-quinonediazidesulfonic acid esters such as phenyl) -1-methylethyl] phenyl) ethane; (poly) hydroxyphenylflavanes, for example, 2,4,4-trimethyl-2 ', 4' 1,2-quinones such as, 7-trihydroxy-2-phenylflavane, 2,4,4-trimethyl-2 ', 4', 5 ', 6,7-pentahydroxy-2-phenylflavane Diazidesulfonic acid esters are particularly suitable.
    The positive and negative photoresist compositions of the present invention optionally comprise one or more additives (c) commonly used in the photoresist, in conventional amounts known to those skilled in the art, such as dyes, pigments, plasticizers, surfactants. , Flow enhancers, wetting agents, adhesion promoters, thixotropic agents, colorants, fillers, dissolution promoters, acid-amplifying agents, photosensitizers and organic basic materials. Further examples of organic basic compounds which can be used in the resist composition of the present invention are compounds which are stronger bases than phenols, in particular nitrogen-containing basic compounds. These compounds may be ionic, for example tetraalkylammonium salts or nonionic. Preferred organic basic compounds are nitrogen-containing basic compounds having at least two nitrogen atoms with different chemical environments per molecule. Particular preference is given to 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 are guanidine, aminopyridine, amino alkylpyridine, aminopyrrolidine, indazole, imidazole, pyrazole, pyrazine, pyrimidine, purine, imidazoline, pyrazoline, piperazine, aminomorpholine and Aminoalkylmorpholine. Both unsubstituted compounds or substituted derivatives thereof are suitable. 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 do. Specific examples of particularly preferred organic basic compounds include guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine , 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2 -Amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) pi Ferridine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyra Sol, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-dia Minopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3- La sleepy, and N- amino-morpholine and N- include (2-aminoethyl) morpholine.
    Other examples of suitable organic basic compounds are DE 4430318, US Pat. No. 5,599,89, US Pat. No. 5,566,734, EP No. 7,762,207, DE No.4306069, EP No. 611998, EP No. 813113, EP No. 611998 and US Pat. 5498506. However, suitable organic basic compounds in the present invention are not limited to the above examples. Nitrogen-containing basic compounds may be used alone or in combination with two or more thereof. The amount of the nitrogen-containing basic compound added is usually 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, per 100 parts by weight of the photosensitive resin composition (excluding the solvent). When the amount thereof is less than 0.001 parts by weight, the effects of the present invention cannot be obtained. On the other hand, if it exceeds 10 parts by weight, reduced photosensitivity and impaired developing ability in the unexposed portions are likely to be caused. The composition is also a basic organic compound which decomposes under actinic radiation, as described, for example, in EP 710885, US 556635, US 5595855, US 5525453 and EP 611998. ["Suicide base"] may also be included.
    Examples of dyes (c) suitable for the compositions of the present invention include fat-soluble dyes and basic dyes, such as 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 (Orien Chemical Industries Ltd., Japan), Crystal Violet (CI 42555), Methyl Violet (CI 42535), Rhodamine B (CI 45170B), Malachite Green (CI 42000) and methylene blue (CI 52015).
    The addition of a spectroscopic sensitizer (e) can be used to increase or decrease the photosensitivity to exhibit absorption in a wavelength region longer than far ultraviolet rays, whereby the photosensitive composition of the invention can be subjected to, for example, i-ray or g-ray irradiation Can be made to respond Examples of suitable spectroscopic sensitizers include benzophenone, p, p'-tetramethyldiaminobenzophenone, p, p'-tetraethylethylaminobenzophenone, thioxanthone, 2-chlorothioxanthone, anthrone, pyrene, Perylene, phenothiazine, benzyl, acridine, orange, benzoflavin, cetoflavin T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5 -Nitroacenaphthene, benzoquinone, 2-chloro-4-nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramid, anthraquinone , 2-ethylanthraquinone, tert-butylanthraquinone, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2 Naphthoquinone, 3-acylcoumarin derivatives, 3,3'-carbonyl-bis (5,7-dimethoxycarbonylcoumarin), 3- (aroylmethylene) thiazolin, eosin, rhodamine, erythrosine and Contains coronene. However, suitable spectroscopic sensitizers are not limited to the above examples.
    The spectroscopic sensitizer can also be used as a light absorber to absorb far ultraviolet rays emitted by the light source. In this case, the light absorber reduces light reflection from the substrate and reduces the influence of multiple reflections in the resist film, thereby reducing the influence of standing waves.
    Further suitable additives (c) are "acid-amplifying agents" which are compounds which promote acid formation or increase acid concentration. Such compounds may also be used in combination with oxime derivatives of the formulas 1, 2 or 3 according to the invention in positive or negative resists, or in phase systems and in all coating applications. Such acid amplifying agents are described, for example, in Arimitsu, K. et al. J. Phtopolym. Sci. Technol. 1995, 8, pp 43; Kudo, K. et al. J. Photopolym. Sci. Technol. 1995, 8, pp 45; Ichimura, K. et al. Chem: Letters 1995, pp 551.
    Typically, for the application of the photosensitive composition of the invention to a substrate, the composition is dissolved in a suitable solvent. Preferred examples of these solvents are ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl Acetates, 2-ethoxyethyl acetate, 2-ethoxyethanol, diethyl glycol dimethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, Ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and tetra Hydrofuran. These solvents can be used alone or as a mixture. Preferred examples of solvents are esters such as 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl methoxypropionate, ethyl ethoxypropionate and ethyl lactate . The use of such solvents is advantageous because the oxime derivatives of the formula (1), (2) or (3) according to the invention have good compatibility with them and have good solubility in them.
    Surfactants may be added to the solvent. Examples of suitable surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene acetyl ether and polyoxyethylene oleyl ether; Polyoxyethylene alkylaryl ethers such as polyoxyethylene, octylphenol ether and polyoxyethylene nonylphenol ether; Polyoxyethylene / polyoxypropylene block copolymers, sorbitan / fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate ; Fluorochemical surfactants such as F-top EF301, EF303 and EF352 (New Akita Chemical Company, Japan), Megafac F171 and F17.3 (Dainippon Ink & Chemicals, Inc., Japan), Fluorad FC 430 and FC431 from Sumitomo 3M Ltd., Japan, Asahi Guard AG710 and Surflon S-382, SC101, SC102, SC103, SC104, SC105 and SC106 from Asahi Grass Col, Ltd., Japan; Organosiloxane polymer KP 341 (Shin-Etsu Chemical Co., Ltd., Japan); And nonionic surfactants such as acrylic or methacrylic acid (co) polymers Poly-flow Nos. 75 and No. 95 (Kyoeisha Chemical Co., Ltd., Japan). The amount of the surfactant added is usually 2 parts by weight or less, preferably 0.5 parts by weight or less per 100 parts by weight of the solid component of the composition of the present invention. The said surfactant can be added individually or in mixture of 2 or more types thereof.
    The solution is uniformly applied to the substrate by known coating methods, for example by spin-coating, dipping, knife coating, curtain pouring technique, brush application, spraying and roller coating. It is also possible to apply the photosensitive layer to a temporary curved support and then to coat the final substrate by coating transfer (laminating). The amount applied (thickness of coating) and the properties of the substrate (coating substrate) depend on the desired application. The range of coating thicknesses in principle comprises values of about 0.01 μm to 100 μm or more.
    After the coating operation, the solvent is generally removed by heating to produce a photoresist layer on the substrate. The drying temperature should of course be below the temperature at which certain components of the resist can react or decompose. In general, the drying temperature is in the range of 60 to 160 ° C.
    Next, the resist coating is subjected to phase-investigation. The term “phase-modal irradiation” refers to irradiation in a predetermined pattern using actinic radiation, ie irradiation through a mask containing a predetermined pattern, eg, transparency, a chrome mask or a reticle, and eg Both irradiation with laser beams or electron beams that write to the resist surface directly under computer control to produce an image. Another way of generating the pattern is by interference of two beams or phases, for example, as used in holographic applications. Further, using a mask made of liquid crystal which may be a pixel addressed by a pixel, see A. Bertsch; J.Y. Jezequel; J.C. Andre, Journal of Photochemistry and Photobiology A: Chemisrty 1997, 107 pp. 275-281 and K.P. Nicolay, Offset Printing 1997, 6, pp. It is possible to create a digital phase as described in 34-37.
    After irradiation and, if necessary, heat treatment, the irradiated areas (for positive resists) or non-irradiated areas (for negative resists) of the composition are removed in a manner known per se using a developer. The coating is preferably heated prior to development in order to facilitate the development of a catalytic reaction, followed by a sufficient difference in solubility between the irradiated and unirradiated areas of the resist coating in the developer. In addition, heating can be performed or initiated during irradiation. The temperature of 60-160 degreeC is used preferably. The time depends on the heating method and, if necessary, the optimum time can be easily determined by several routine experiments by one skilled in the art. Generally from a few seconds to a few minutes. For example, when using a hot plate, a time of 10 to 300 seconds is very suitable, and when using a convection oven, a time of 1 to 30 minutes is very suitable. It is important that the latent donor according to the invention is stable under the processing conditions in the area not irradiated on the resist.
    The coating is developed to remove a portion of the coating that is more soluble in the developer after irradiation. If necessary, slight agitation of the workpiece, mild brushing or spraying of the coating in the developer bath may speed up the process step. Aqueous-alkali developers conventional in resist technology can be used, for example, for development. Such developers are, for example, sodium or potassium hydroxide, the corresponding carbonates, hydrogen carbonates, silicates or metasilicates, preferably metal-free bases such as ammonia or amines such as ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyl diethylamine, alkanolamines, for example dimethyl ethanolamine, triethanol amine, quaternary ammonium hydroxide, for example tetra Methylammonium hydroxide or tetraethylammonium hydroxide. The developer is generally 0.5 N or less, but is usually diluted by a suitable method before use. For example, a solution having a normal concentration of about 0.1 to 0.3 is sufficiently suitable. The choice of developer depends on the nature of the photocurable surface coating, in particular on the binder used or on the resulting photolysis product. The developer aqueous solution may also contain a relatively small amount of a wetting agent and / or an organic solvent, if necessary. Typical organic solvents that can be added to the developer emulsion are, for example, cyclohexanone, 2-ethoxyethanol, toluene, acetone, isopropanol, and mixtures of two or more of these solvents. Typical aqueous / organic developer systems are based on Butylcellosolve RTM / water.
    It is also an object of the present invention to provide a method for preparing a substrate comprising the steps of: (1) applying the above composition to a substrate; (2) baking the composition at a temperature of 60 to 160 ° C. after application; (3) phase-mode irradiation with light rays of wavelengths from 150 to 1500 nm; (4) optionally baking the composition at a temperature of 60 to 160 ° C. after exposure; And (5) developing using a solvent or an aqueous alkaline developer to produce a photoresist.
    Preference is given to conducting the phase-in mode irradiation using mono or polychromatic irradiation in the wavelength range 190 to 450 nm, in particular in the wavelength range 190 to 260 nm.
    The photoresist according to the invention has excellent lithographic properties, in particular high photosensitivity, and high resist transparency to phase irradiation.
    The areas in which the compositions according to the invention can be used are as follows: for photosensitive resists for electronics, for example integrated circuits or thin film transistor- resists (TFTs) as etch resists, electroplating resists or solder resists. Produce; Production of printing plates, eg offset printing plates or screen printing templates, etching of castings or use in stereolithography or holographic techniques. The coating substrate and the processing conditions change accordingly.
    The compositions according to the invention also contain wood, textiles, paper, ceramics, glass, plastics, for example polyesters, polyethylene terephthalates, polyolefins or cellulose acetates, in particular in the form of membranes, which are applied by phase-wise irradiation. It is very suitable as a coating composition for all types of substrates, in particular coating metals, for example Ni, Fe, Zn, Mg, Co or especially Cu and Al, and also Si, silicon oxide or silicon nitride.
    The present invention also relates to the use of the compounds of formula 1b, 2b or 3b as photolattic acid donors in compositions capable of crosslinking under the action of an acid and / or as dissolution enhancers in compositions in which solubility increases under the action of an acid.
    It is also an object of the present invention to add a compound of formulas 1b, 2b and / or 3b to the compounds described above to crosslink under the action of an acid, irradiating in a phase manner or with light having a wavelength of 150 to 1500 nm over the entire region. It is a crosslinking method of a compound which can be bonded. The present invention also provides formulas 1b, 2b or 3b as photosensitive acid donors in the preparation of surface coatings, printing inks, printing plates, dental compositions, color filters, resists or phase-recording materials, or phase-recording materials for holographic image recording. The use of the compound of the present invention, and a method for producing a surface coating, printing ink, printing plate, dental composition, color filter, resist or image-recording material, or phase-recording material for holographic image recording. The object of the present invention also relates to the use of a compound of formula 1, 2 or 3 as photosensitive acid donor in the production of color filters or chemically amplified resist materials.
    As already mentioned above, in the photocrosslinkable composition, the oxime derivatives act as curable latent catalysts: when irradiated with light, they release an acid which catalyzes the crosslinking reaction. In addition, the acid released by irradiation can catalyze, for example, the removal of suitable acid-sensitive protecting groups from the polymer structure or the degradation of polymers containing acid-sensitive groups in the polymer backbone. Other applications are, for example, color-change systems based on changes in pH or solubility of pigments protected by acid-sensitive protective groups.
    The oxime derivatives according to the invention can also be used as compounds, for example chromosomes, which change color when the pH changes as described in JP 1984 4328-A or US 5237059. When used with, it can be used to create so-called "print-out" phases. Such color-changing systems can also be used in accordance with EP 199672 to monitor products which are sensitive to heat or radiation. In addition to the color change, pigment crystals can be precipitated during acid-catalyzed deprotection of soluble pigment molecules (eg as described in EP 648770, EP ash 648817 and EP 742255): If the color of the latent pigment precursor is different from the color of the precipitated pigment crystals, it can be used, for example, in the preparation of color fillers or in the application of print out images and indicators, as described in EP 654711. .
    Compositions using pH sensitive dyes or latent pigments in combination with oxime derivatives can be used as electromagnetic radiation, for example gamma irradiation, electron beams, indicators for ultraviolet or visible light, or as simple waste dosimeters. Particularly of interest are the dosimeters described above, in the case of light rays which are invisible to the human eye, for example ultraviolet or infrared light.
    Finally, oxime derivatives that are poorly soluble in aqueous-alkaline developers are made to be soluble in the developer by light-induced conversion to the free acid, which in turn can be used as a dissolution promoter with a suitable film-forming resin.
    Resins that can be crosslinked by acid catalysis and thus photolated acids of the compounds of formulas 1, 2 or 3, in particular of formulas 1b or 3b, are for example polyfunctional alcohols or hydroxy-group-containing Acrylic resins and polyester resins, or mixtures of partially hydrolyzed polyvinyl acetals or polyvinyl alcohols with polyfunctional acetal derivatives. Under certain conditions, for example, acid-catalyzed self-condensation of acetal-functionalized resins is also possible.
    Suitable acid-curable resins are generally all resins, for example aminoplast or phenolic resol resins, wherein the curing can be facilitated by an acid catalyst. These resins are, for example, melamine, urea, epoxy, phenol, acrylic, polyester and alkyd resins, in particular acrylic, polyester or mixtures of alkyd and melamine resins. Also included are modified surface-coating resins such as acrylic-modified polyesters and alkyd resins. Examples of each type of resin included in the terms acrylic, polyester and alkyd resins are described, for example, in Wagner, Sarx, Lackkunstharze (Munich, 1971), pp. 86-123 and 229-238, or 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 are esterified or non-esterified melamine, urea, guanidine or biuret resins. Acid catalysis is particularly hardening of surface coatings comprising esterified amino resins such as methylated or butylated melamine resins (N-methoxymethyl- or N-butoxymethyl-melamine) or methylated / butylated glycolurils. Is important. Examples of other resin compositions include polyfunctional alcohols or hydroxy-group-containing acrylic and polyester resins, or partially hydrolyzed polyvinyl acetates or polyvinyl alcohols with polyfunctional dihydropropanyl derivatives such as 3, There is a mixture of derivatives of 4-dihydro-2H-pyran-2-carboxylic acid. Polysiloxanes can also be crosslinked by acid catalysis. These siloxane group-containing resins can be self-condensed, for example, by acid-catalyzed hydrolysis or can be the second component of the resin, for example polyfunctional alcohols, hydroxy-group-containing acrylic or polyester resins. And crosslinked with partially hydrolyzed polyvinyl acetal or polyvinyl alcohol. The type of polycondensation of such polysilonic acids is described, for example, in J.J. Lebrun, H. Pode, Comprehensive Polymer Science, Vol. 5, p. 593, Pergamon Press, Oxford, 1989. Other cationic polymerizable materials suitable for the preparation of surface coatings are ethylenically unsaturated compounds polymerizable by cationic mechanisms, such as vinyl ethers such as methyl vinyl ether, isobutyl vinyl ether, trimethylolpropane trivinyl Ethers, ethylene glycol divinyl ethers; 3,4 of cyclic vinyl ethers such as 3,4-dihydro-2-formyl-2H-pyran (dimer acrolein) or 2-hydroxymethyl-3,4-dihydro-2H-pyran -Dihydro-2H-pyran-2-carboxylic acid ester; Vinyl esters such as vinyl acetate and vinyl stearate, mono- and di-olefins such as α-methylstyrene, N-vinylpyrrolidone or N-vinylcarbazole.
    For certain purposes, resin mixtures having monomeric or oligomeric components containing polymerizable unsaturated groups are used. Such surface coatings can also be cured using the compounds of the formulas (1), (2) or (3). In this process, radical polymerization initiators or photoinitiators may be further used. The former initiates the polymerization of unsaturated groups during heat treatment and the latter initiates during UV irradiation.
    In addition, the present invention (a) a compound which hardens upon the action of the acid or increases the solubility upon the action of the acid; And (b) at least one compound of formula 1b, 2b or 3b as described above as photosensitive acid donor.
    The compounds of formula 1, 2 or 3, or 1b, 2b or 3b may each be added to the composition in an amount of generally 0.1 to 30% by weight, for example 0.5 to 10% by weight, in particular 1 to 5% by weight.
    According to the invention, a compound of formula 1, 1b, 2, 2b, 3 or 3b is combined with an additional photosensitive acid donor compound (b1), an additional photoinitiator (d), a sensitizer (e) and / or an additive (c) Can be used together Suitable photosensitive acid donor compounds (b1), sensitizers (e) and additives (c) are as described above.
    Examples of further photoinitiators (d) are radical photoinitiators such as benzophenone, acetophenone derivatives such as α-hydroxycycloalkylphenyl ketones, dialkoxyacetophenones, α-hydroxy- or α-amino Acetophenone, 4-aroyl-1,3-dioxolane, benzoin alkyl ether and benzyl ketal, monoacylphosphine oxide, bisacylphosphine oxide or titanocene. Examples of further suitable photoinitiators which are particularly suitable are: 1- (4-dodecylbenzoyl) -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, phenyl-1-hydroxycyclohexyl ketone, (4-morpholinobenzoyl) -1 -Benzyl-1-dimethylamino-propane, 1- (3,4-dimethoxyphenyl) -2-benzyl-2-dimethylamino-butan-1-one, (4-methylthiobenzoyl) -1-methyl-1 -Morpholino-ethane, benzyl dimethyl ketal, bis (cyclopentadienyl) -bis (2,6-difluoro-3-furyl-phenyl) titanium, trimethylbenzoyldiphenylphosphine oxide, bis (2,6 -Dimethoxy-benzoyl)-(2,4,4-trimethyl-pentyl) -phosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-dipentyloxyphenyl-force Oxide or bis (2,4,6-trimethylbenzoyl) phenyl-phosphine oxide. Further suitable photoinitiators can be found in US Pat. No. 4,505,81, column 20, row 35 to column 21, row 35. Other examples are trihalomethyltriazine derivatives or hexaarylbisimidazolyl compounds. Further examples of further photoinitiators are borate compounds as described, for example, in US Pat. No. 4,472,530, EP 775706, GB 2307474, GB 2307473 and GB 2304472. The borate compound is preferably used with an electron acceptor compound, for example a dye cation, or a thioxanthone derivative.
    Further examples of further photoinitiators are peroxide compounds, for example benzoyl peroxide (other suitable peroxides are described in US Pat. No. 4,505,81, 19, paragraphs 17 to 25) or cationic photoinitiators, for example aromatic sulfides. Phonium or iodonium salts, for example those found in US Pat. No. 4,505,81, 18th, 60th to 19th, 10th row, or cyclopentadienyl-arene-iron (II) complex salts, eg For example, (η 6 -isopropylbenzene) (η 5 -cyclopentadienyl) -iron (II) hexafluorophosphate.
    Surface coatings may be surface-coated resin solutions or suspensions in organic solvents or water, but they may also be solvent-free. Of particular interest are surface coatings having a low solvent content, so-called "high solid surface coatings", and powder coating compositions. The surface coating can be, for example, a transparent lacquer used in the automotive industry as a finishing lacquer for multilayer coatings. They may also comprise pigments and / or fillers which may be inorganic or organic compounds, and metal powders for metal effect finishing.
    Surface coatings may also comprise relatively small amounts of certain additives customary in surface-coating techniques, such as fluidity improvers, thixotropic agents, leveling agents, forge agents, wetting agents, adhesion promoters, light stabilizers, antioxidants or sensitizers. Can be.
    UV absorbers such as hydroxyphenyl-benzotriazole, hydroxyphenyl-benzophenone, oxalic acid amide or hydroxyphenyl-s-triazine type can be added to the compositions according to the invention as light stabilizers. Each compound or mixture of these compounds can be used with or without addition of steric hindrance amines (HALS).
    Examples of such UV absorbers and light stabilizers are as follows:
    1. 2- (2'-hydroxyphenyl) benzotriazole, for example 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole, 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-benzo Triazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-5'-tertiary -Butyl-2'-hydroxyphenyl) -benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) -benzotriazole, 2- (3 ', 5'-di-tert- Amyl-2'-hydroxyphenyl) -benzotriazole, 2- (3 ', 5'-bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl) -benzotriazole, and 2- (3 'Tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-5'- [2- (2-ethyl-hexyloxy) -carbonylethyl] -2'-high Oxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) -5-chloro-benzotria Sol, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) -benzotriazole, 2- (3'-tert-butyl-2 '-Hydroxy-5'-(2-octyloxycarbonylethyl) phenyl) -benzotriazole, 2- (3'-tert-butyl-5 '-[2- (2-ethylhexyloxy) carbo Nylethyl] -2'-hydroxyphenyl) -benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) -benzotriazole and 2- (3'-tertiary- Butyl-2'-hydroxy-5 '-(2-isooctyloxycarbonylethyl) phenyl-benzotriazole, 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl ) -6-benzotriazol-2-yl-phenol]; 2- [3'-tert-butyl-5 '-(2-methoxycarbonylethyl) -2'-hydroxy-phenyl]- Transesterification product of benzotriazole with polyethylene glycol 300; [R-CH 2 CH 2 -COO (CH 2 ) 3 ] 2- , wherein R is 3'-tert-butyl-4'-hydroxy- 5 ' -2H-benzotriazol-2-yl-phenyl).
    2. 2-hydroxybenzophenones such as 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 acid, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert- Butylbenzoyl) resorcinol, 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. Acrylate, for example α-cyano-β, β-diphenylacrylic acid ethyl ester or isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester, α-cyano-β-methyl-p- Methoxy-cinnamic acid methyl ester or butyl ester, α-carbomethoxy-p-methoxy-cinnamic acid methyl ester, N- (β-carbomethoxy-β-cyanovinyl) -2-methyl-indole.
    5. Stereohindered 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, N, N ' Condensation of bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine with 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine Product, tris (2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, 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-penta Tilpiperidyl) -2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl -1,3,8-triazaspiro [4.5] decane-2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyl Oxy-2,2,6,6-tetramethylpiperidyl) succinate, N, N'-bis (2,2,6,6-tetra-methyl-4-piperidyl) hexamethylenediamine and 4- Condensation product of morpholino-2,6-dichloro-1,3,5-triazine, 2-chloro-4,6-di (4-n-butylamino-2,2,6,6-tetramethylpy Condensation product of ferridyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, 2-chloro-4,6-di (4-n-butylamino-1,2 Condensation product of 2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7 , 7,9,9-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-oxanilide, 2,2-di-octyloxy-5,5'-di -Tert-butyl-oxanilide, 2,2'-didodecyloxy-5,5'-poly-tert-butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N, N'-bis (3-dimethylaminopropyl) oxanilide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and 2-ethoxy-2'-ethyl-5, Mixtures with 4'-di-tert-butyl-oxanilide, mixtures of o- and p-methoxy- and o- and p-ethoxy-di-substituted oxanilides.
    7. 2- (2-hydroxyphenyl) -1,3,5-triazine, for example 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5 -Triazine, 2- (2-hydroxy-4-octyloxyphenyl) -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-propyloxyphenyl) -6- (2 , 4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -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-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxy-propyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-dodecyl- / tri Decyl-oxy- (2-hydroxypropyl) oxy-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl)- 1,3,5-triazine.
    8. phosphites and phosphonites such as triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, Distearyl-pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol 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-butylphenyl) pentaerythritol diphosphite, tristearyl-sorbitol triphosphite, tetrakis (2 , 4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tet -Tert-butyl-12H-dibenzo [d, g] -1,3,2-dioxaphosphosine, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl -Dibenzo [d, g] -1,3,2-dioxaphosphosine, bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis (2,4-di-3 Tert-butyl-6-methylphenyl) ethyl phosphite.
    The light stabilizers can also be added, for example, to adjacent surface-coating layers, which gradually diffuse into the layer of stoving lacquer to be protected therefrom. The adjoining surface-coating layer may be a stoving lacquer or a primer under the finishing lacquer on the stoving lacquer.
    It is also possible to add, to the resin, a photosensitizer, for example, by varying or increasing the spectral sensitivity to reduce the irradiation period and / or to use other light sources. Examples of photosensitizers include aromatic ketones or aromatic aldehydes (as described, for example, in US4017652), 3-acyl-coumarins (eg, US 4366228, EP 738928, EP 22188). As described), keto-coumarins (as described, for example, in US Pat. No. 5,346,333, EP 538997, JP 08272095-A), styryl-coumarins (as described, for example, in EP 624580). ), 3- (aroylmethylene) -thiazoline, thioxanthone, condensed aromatic compounds such as perylene, aromatic amines (eg US Pat. No. 4069954 or WO 96/41237) As described in) or cationic and basic colorants (eg as described in US Pat. No. 4026705), for example eosin, rhodanine and erythrosin colorants, and for example JP 8320551-. A, EP 747771, JP 7036179-A, EP 619520, JP 6161109-A, JP 606044141, JP 6060198-A, WO 93/15440, EP 568993 , JP 5005005-A, JP 50202742-A, JP 55301910-A, JP 4004010-A, JP 4294148-A, EP 359431, EP 103294, US 4262309, Dyes and pigments as described in EP 39825, EP 5274, EP 727713, EP 726497 or DE 2027467.
    Other conventional additives depend on the intended use—optical bleach, filler, pigment, pigment, wetting agent or flow improver and adhesion promoter.
    In order to cure thick, pigmented coatings it is suitable to add fine glass beads or powder glass fibers as described in US Pat. No. 50,13,768.
    Oxime derivatives can also be used as hybrid systems. This system is based on a structure that is fully cured by two different reaction mechanisms. Examples thereof are systems which include components capable of carrying out acid catalyzed crosslinking or neutralization reactions, but also comprising additional components which crosslink by the second mechanism. Examples of the second mechanism are radical full cure, oxidative crosslinking or moisture-initiated crosslinking. The second curing mechanism can be initiated purely with heat, optionally with a suitable catalyst, or by light rays using a second photoinitiator. Suitable further photoinitiators are as described above.
    When the composition comprises a radically crosslinkable component, the curing method is particularly a method of curing a pigmented composition (e.g. with titanium dioxide), which component forms a radical under thermal conditions, for example azo compounds. For example 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), triazene, diazosulfide, pentazadiene or peroxide compounds such as hydrogen peroxide or peroxycarbonate, For example by the addition of tert-butyl hydrogen peroxide described in EP 245639. The addition of redox initiators, such as cobalt salts, aids in curing by oxidative crosslinking with oxygen from air.
    Surface coating may be applied by one of the conventional methods in the art, for example by spraying, painting or dipping. If a suitable surface coating is used, electrical applications, for example cathodic electrophoretic deposition, are also possible. After drying, the surface coating film is irradiated. In some cases, the surface coating film is completely cured by heat treatment.
    Compounds of formula (1), (2) or (3) can also be used in cured moldings made of composites. The composite consists of a self-supporting matrix material, for example a glass fiber fabric impregnated with a photocurable structure.
    It is known from EP 592139 that oxime derivatives can be used as acid generators which can be activated by light in compositions suitable for the surface treatment and cleaning of glass, aluminum and steel surfaces. The use of such compounds in organosilane systems results in compositions having significantly better storage stability than those obtained when free acids are used. Compounds of formula 1, 2 or 3 are also suitable for this application.
    The oxime derivatives of the present invention can also be used to shape polymers that undergo acid induced transition reactions in the state of having the required physical properties using photographic plates. For example, oxime derivatives are described, for example, in M.L. Renak; C. Bazan; D. Roitman; Advanced materials 1997, 9, 392, can be used to pattern conjugated spinning polymers. Such patterned emissive polymers can be used to make microscalar patterned light emitting diodes (LEDs) that can be used to make displays and data storage media. In a similar manner patterning precursors for polyimides (e.g., polyimide precursors having acid labile protecting groups that change solubility in a developer) and can be provided as protective coatings in the manufacture of microchips and printed circuit boards. The polyimide layer, the insulating layer, and the buffer layer can be formed.
    The structures of the present invention can also be used as stress buffer layers in the manufacture of conformal coatings, optical imaging layers and dielectrics, integrated circuits as they are used in continuous construction systems for printed circuit boards.
    It is known that conjugated polymers, such as polyaniline, can be converted from semiconductor to conductor state by proton doping. The oxime derivatives of the present invention can also be used in topographic investigation compositions comprising such conjugated polymers to form conductor structures (exposed regions) enclosed in insulating materials (non-exposed regions). Such materials can be used as leads and connections for the manufacture of electrical and electronic devices.
    Suitable radiation sources for compositions comprising the compounds of formula 1, 2 or 3 include irradiation of wavelengths of about 150 to 1500, for example 180 to 1000, preferably 190 to 700 nm, as well as e-beams such as X-rays and high -A source of energy that emits electromagnetic radiation. Both point sources and flat projectors (lamp carpets) are suitable. Examples include: carbon arc lamps randomly doped with metal halides, xenon arc lamps, medium pressure, high and low pressure mercury lamps (metal halide lamps), ultrashort-excited metal vapor lamps, excimer lamps, ultra-fluorescent fluorescent tubes, Electron beams and X-ray beams generated by fluorescent lamps, argon filament lamps, electronic flash lamps, photographic flood lights, synchrotrons or laser plasmas. The distance between the irradiator and the undercoating layer according to the invention to be irradiated may vary, for example, from 2 cm to 150 cm depending on the intended use and the type and / or strength of the irradiator. Suitable sources of radiation are in particular mercury vapor lamps, in particular medium and high pressure mercury lamps, from which radiation of other wavelengths can be filtered, if desired. This is especially true for relatively short wavelength irradiation. However, it is also possible to use low energy lamps (e.g. fluorescent tubes) that can be emitted in a suitable wavelength range. An example of this is the Philips TL03 lamp. Another type of radiation source that can be used is a light emitting diode (LED) that emits different wavelengths across the entire spectrum as narrow band radiation sources or light band (white light) sources. Laser sources such as excimer lasers, for example Kr-F lasers for irradiation at 248 nm, Ar-F lasers at 193 nm, F 2 lasers at 157 nm are suitable. Lasers in the visible and infrared ranges may also be used. Irradiation of mercury i, h and g rays at wavelengths of 365, 405 and 436 nm is particularly suitable. Suitable laser-beam sources are, for example, argon-ion lasers, which emit radiation of wavelengths of 454, 458, 466, 472, 478, 488 and 514 nm. Nd-YAG-lasers that emit 1064 nm light and their second and third harmonics (532 nm and 355 nm, respectively) can also be used. For example, helium / cadmium lasers emitting at 442 nm or lasers emitting in the ultraviolet range are also suitable. With this type of irradiation, it is not necessary to use photomasks with photopolymerizable coatings to produce positive or negative resists; The controlled laser beam can write directly onto the coating. For this purpose, the highly sensitive material according to the invention, which enables a high writing speed at a relatively low intensity, is very advantageous. Upon irradiation, the oxime derivative in the composition at the irradiated portion of the surface coating decomposes to form an acid.
    Unlike the case of conventional ultraviolet light, which hardens with high-intensity radiation, the compound according to the invention is activated under the action of relatively low intensity radiation. Suitable irradiation includes, for example, daylight (sunlight), and radiation sources corresponding to daylight. Sunlight is different in light and spectral composition and intensity of artificial irradiation sources commonly used for ultraviolet curing. The absorption properties of the compounds according to the invention are also suitable for developing sunlight as a natural source of radiation for curing. Sun-corresponding artificial light sources that can be used to activate the compounds according to the invention are to be understood as low intensity projectors, for example any fluorescent lamps, for example Philips TL05 specific fluorescent lamps or Philips TL09 specific fluorescent lamps. Lamps having a high daylight content and daylight itself can in particular harden the surface of the surface-coating layer in a tack-free manner. In this case an expensive curing device is not necessary and the composition can be used in particular for external finishing. Curing with daylight or sun-corresponding light sources is an energy-saving method and prevents the release of volatile organic components in external applications. In contrast to conveyor belt methods suitable for flat components, daylight curing can also be used for external finishing of static or fixed products and structures.
    The surface coating to be cured can be exposed directly to sunlight or a sun-compatible light source. However, curing can also occur under transparent layers (eg, glass or plastic sheets).
    The following examples illustrate the invention in more detail. Unless stated otherwise, parts and percentages are by weight, as in the remainder of the description and in the claims. Alkyl radicals having 3 or more carbon atoms mean in each case n-isomers unless otherwise specified.
    Example 1 2,2,2-trifluoro-1-phenyl-ethanone oxime-O-methylsulfonate
    1.1: 2,2,2-trifluoro-1-phenyl-ethanone oxime
    25 g (0.144 mol) of 2,2,2-trifluoro-1-phenyl-ethanone are dissolved in 40 ml of ethanol at 80 ° C. 10.5 g (0.151 mol) of hydroxylammonium chloride and 20.1 g (0.245 mol) of sodium acetate dissolved in 20 ml of water are added dropwise to the solution. The reaction mixture is refluxed overnight and the solvent is distilled off on a rotary evaporator. The residue is poured into water, the white precipitate is washed with water, dried under vacuum and 24.4 g of 2,2,2-trifluoro-1-phenyl-ethanone oxime is obtained. The crude product is used in the next step without further purification.
    1.2: 2,2,2-trifluoro-1-phenyl-ethanone oxime-O-methylsulfonate
    2.0 g (10.6 mmol) of 2,2,2-trifluoro-1-phenyl-ethanone oxime are dissolved in 40 ml of tetrahydrofuran (THF) and cooled in an ice bath. To this solution is added 1.3 g (11.7 mmol) of methylsulfonyl chloride followed by the dropwise addition of 1.6 g (15.9 mmol) of triethylamine. The reaction mixture is stirred at 0 ° C. for 5 hours, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by reprecipitation using methanol and water, and 2.3 g (8.6 mmol; 81%) of 2,2,2-trifluoro-1-phenyl-ethanone oxime-O- (methanesulfonate) was added. Obtained as a white solid (melting point (mp) 51-64 ° C.).
    The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). [pm]: 3.26 (s, 3 H), 7.47-7.63 (m, 5 H).
    Example 2: 2,2,2-trifluoro-1-phenyl-ethanone oxime-O- (10-camphorylsulfonate)
    2.0 g (10.6 mmol) of 2,2,2-trifluoro-1-phenyl-ethanone oxime (prepared as described in Example 1.1) are dissolved in 40 ml of THF and cooled in an ice bath. To this solution is added 2.9 g (11.6 mmol) of 10-camphorylsulfonyl chloride followed by the dropwise addition of 1.6 g (15.9 mmol) of triethylamine. The reaction mixture is stirred at 0 ° C. for 2.5 h, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by flash chromatography on silica gel using ethyl acetate and hexane (1: 9) as eluent, and 2.2 g (5.5 mmol; 52%) of 2,2,2-trifluoro-1-phenyl- Ethanone oxime-O- (10-camphorylsulfonate) is obtained as a pale yellow liquid. The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 0.92 (s, 3H), 1.14 (Z) /1.18 (E) (s, 3H), 1.40-1.50 (m, 1H), 1.66-1.75 (m, 1H), 1.92-2.19 (m , 3H), 2.34-2.55 (m, 2H), 3.28 (E) /3.33 (Z) (d, 1H), 3.87 (Z) /3.97 (E) (d, 1H), 7.48-7.65 (m, 5H ). 1 H-NMR shows that the product is a mixture of 9: 1 Z and E isomers. Signals are temporarily designated as E- and Z-structures.
    Example 3: 2,2,2-trifluoro-1-phenyl-ethanone oxime-O- (4-methoxyphenylsulfonate)
    2.0 g (10.6 mmol) of 2,2,2-trifluoro-1-phenyl-ethanone oxime (prepared as described in Example 1.1) are dissolved in 40 ml of THF and cooled in an ice bath. To this solution is added 2.4 g (11.7 mmol) of 4-methoxyphenylsulfonyl chloride followed by the dropwise addition of 1.6 g (15.9 mmol) of triethylamine. The reaction mixture is stirred at 0 ° C. for 5 hours, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by recrystallization from methanol and 2.3 g (6.5 mmol; 61%) of 2,2,2-trifluoro-1-phenyl-ethanone oxime-O- (4-methoxyphenylsulfonate) Is obtained as a white solid (mp. 69-73 ° C.). The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 3.92 (s, 3H), 7.05 (d, 2H), 7.38-7.58 (m, 5H), 7.95 (d, 2H).
    Example 4: 2,2,2-trifluoro-1-phenyl-ethanone oxime-O- (1-naphthylsulfonate)
    2.0 g (10.6 mmol) of 2,2,2-trifluoro-1-phenyl-ethanone oxime (prepared as described in Example 1.1) are dissolved in 40 ml of THF and cooled in an ice bath. To this solution is added 2.6 g (11.6 mmol) of 1-naphthylsulfonyl chloride and then 1.6 g (15.9 mmol) of triethylamine are added dropwise. The reaction mixture is stirred at 0 ° C. for 4 h, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by reprecipitation using acetone and water and 3.7 g (9.8 mmol; 92%) of 2,2,2-trifluoro-1-phenyl-ethanone oxime-O- (1-naphthylsulfo Nate) is obtained as a white solid (melting point, 96-104 ° C.). The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). [pm]: 7.23-7.38 (m, 2H), 7.43-7.85 (m, 6H), 7.95-8.05 (m, 1H), 8.18-8.27 (m, 1H), 8.37-8.83 (m, 2H).
    Example 5: 2,2,2-trifluoro-1-phenyl-ethanone oxime-O- (2-naphthylsulfonate)
    2.0 g (10.6 mmol) of 2,2,2-trifluoro-1-phenyl-ethanone oxime (prepared as described in Example 1.1) are dissolved in 40 ml of THF and cooled in an ice bath. To this solution is added 2.6 g (11.6 mmol) of 2-naphthylsulfonyl chloride followed by the dropwise addition of 1.6 g (15.9 mmol) of triethylamine. The reaction mixture is stirred at 0 ° C. for 4 h, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by recrystallization from methanol and 2.8 g (7.4 mmol; 70%) of 2,2,2-trifluoro-1-phenyl-ethanone oxime-O- (2-naphthylsulfonate) Is obtained as a white solid (melting point, 117-120 ° C.). The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 7.37-7.58 (m, 5H), 7.64-7.78 (m, 2H), 7.92-8.09 (m, 4H), 8.63 (s, 1H).
    Example 6: 2,2,2-trifluoro-1-phenyl-ethanone oxime-O- (2,4,6-trimethylphenylsulfonate)
    2.0 g (10.6 mmol) of 2,2,2-trifluoro-1-phenyl-ethanone oxime (prepared as described in Example 1.1) are dissolved in 40 ml of THF and cooled in an ice bath. 2.5 g (11.6 mmol) of 2,4,6-trimethylphenylsulfonyl chloride are added to this solution, followed by the dropwise addition of 1.6 g (15.9 mmol) of triethylamine. The reaction mixture is stirred at 0 ° C. for 4.5 h, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by reprecipitation using methanol and water, and 3.2 g (8.6 mmol; 81%) of 2,2,2-trifluoro-1-phenyl-ethanone oxime-O- (2,4,6 -Trimethylphenylsulfonate) is obtained as a white solid (mp 90-103 ° C.). The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 2.34 (E) /2.36 (Z) (s, 3H), 2.60 (Z) /2.68 (E) (s, 6H), 7.00 (m, 2H), 7.40 (s, 2H), 7.47 -7.58 (m, 3 H). 1 H-NMR shows that the product is a mixture of 4: 1 Z and E isomers. Signals are temporarily designated as E- and Z-structures.
    Example 7: 2,2,2-trifluoro-1- (4-methylphenyl) -ethanone oxime-O- (10-camphorylsulfonate)
    7.1: 2,2,2-trifluoro-1- (4-methylphenyl) -ethanone
    50.0 g (0.543 mol) toluene and 66.3 g (0.543 mol) 4-dimethylaminopyridine are mixed in 700 ml of CH 2 Cl 2 and cooled in an ice bath. To this solution is added 114.0 g (0.543 mol) of trifluoroacetic anhydride, followed by dropwise addition of 167 g (1.25 mol) of AlCl 3 in portions. The reaction mixture is stirred at rt overnight, poured into ice water and extracted with CH 2 Cl 2 . The organic phase is washed with water, dried over MgSO 4 and concentrated. The residue is distilled at 90 ° C./15 mm Hg and 49.5 g of product are obtained as a colorless liquid.
    7.2: 2,2,2-trifluoro-1- (4-methylphenyl) -ethanone oxime
    49.5 g (0.263 mol) of 2,2,2-trifluoro-1- (4-methylphenyl) -ethanone is dissolved in 250 ml of ethanol at 80 ° C. 19.2 g (0.276 mol) of hydroxylammonium chloride and 36.7 g (0.447 mol) of sodium acetate dissolved in 125 ml of water are added dropwise to this solution. The reaction mixture is refluxed for 3.5 hours. The mixture is poured into ice water and a white solid is obtained. Filtration yields 39.2 g of 2,2,2-trifluoro-1- (4-methylphenyl) -ethanone oxime as a white solid (m. P. 54-68 ° C.). The crude product is used in the next step without further purification.
    7.3: 2,2,2-trifluoro-1- (4-methylphenyl) -ethanone oxime-O- (10-camphorylsulfonate)
    3.0 g (14.8 mmol) of 2,2,2-trifluoro-1- (4-methylphenyl) -ethanone oxime are dissolved in 30 ml of THF and cooled in an ice bath. To this solution is added 4.1 g (16.2 mmol) of 10-camphorylsulfonyl chloride followed by the dropwise addition of 2.3 g (22.2 mmol) triethylamine. The reaction mixture is stirred at 0 ° C. for 90 minutes, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by flash chromatography on silica gel using ethyl acetate and hexane (1: 9) as eluent, and 3.2 g (7.7 mmol; 52%) of 2,2,2-trifluoro-1- (4 -Methylphenyl) -ethanone oxime-O- (10-camphorylsulfonate) is obtained as a colorless liquid. The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 0.92 (s, 3H), 1.14 (Z) /1.18 (E) (s, 3H), 1.42-1.50 (m, 1H), 1.64-1.74 (m, 1H), 1.93-2.18 (m , 3H), 2.35-2.56 (m, 5H), 3.28 (E) /3.33 (Z) (d, 1H), 3.87 (Z) /3.94 (E) (d, 1H), 7.27-7.32 (m, 2H ), 7.43 (Z) /7.53 (E) (d, 2H). 1 H-NMR shows that the product is a mixture of 4: 1 Z and E isomers. Signals are temporarily designated as E- and Z-structures.
    Example 8: 2,2,2-trifluoro-1- (4-methylphenyl) -ethanone oxime-O- (methylsulfonate)
    3.0 g (14.8 mmol) of 2,2,2-trifluoro-1- (4-methylphenyl) -ethanone oxime (prepared as described in Example 7.2) are dissolved in 30 ml of THF and cooled in an ice bath. . To this solution is added 1.9 g (16.2 mmol) of methylsulfonyl chloride and then 2.3 g (22.2 mmol) triethylamine are added dropwise. The reaction mixture is stirred at 0 ° C. for 4 h, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by flash chromatography on silica gel using ethyl acetate and hexanes (15:85) as eluent, and 2.6 g (9.2 mmol; 62%) of 2,2,2-trifluoro-1- (4 -Methylphenyl) -ethanone oxime-O- (methylsulfonate) is obtained as a white solid (melting point: 56-67 ° C). The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). [pm]: 2.42 (s, 3 H), 3.27 (s, 3 H), 7.26-7.53 (m, 4 H).
    Example 9: 2,2,2-trifluoro-1- (2-methylphenyl) -ethanone oxime-O- (10-camphorylsulfonate)
    9.1: 2,2,2-trifluoro-1- (2-methylphenyl) -ethanone
    Grignard reagent is prepared from 25.0 g (0.146 mol) of 2-bromotoluene and 4.3 g (0.175 mol) of magnesium in 100 ml of diethyl ether. The Grignard reagent is added dropwise at -78 ° C to a solution of 22.8 g (0.161 mol) of ethyl trifluoroacetate in 120 ml of diethyl ether. The reaction mixture is allowed to warm up to room temperature and stirred for an additional 1 hour. 300 ml of aqueous NH 4 Cl solution and 100 ml of 1N HCl are added to the mixture. The aqueous phase is removed and the organic phase is washed with aqueous NH 4 Cl solution and brine, dried over MgSO 4 and concentrated. The residue is purified by flash chromatography on silica gel using hexane as eluent to afford 6.3 g of 2,2,2-trifluoro-1- (2-methylphenyl) -ethanone as a colorless liquid.
    9.2: 2,2,2-trifluoro-1- (2-methylphenyl) -ethanone oxime
    3.7 g (0.020 mol) of 2,2,2-trifluoro-1- (2-methylphenyl) -ethanone is dissolved in 20 ml of ethanol at 80 ° C. To this solution is added dropwise 1.4 g (0.020 mol) of hydroxylammonium chloride and 2.7 g (0.033 mol) of sodium acetate in 10 ml of water. The reaction mixture is refluxed for 5 hours, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 , concentrated and 2.7 g of 2,2,2-trifluoro-1- (2-methylphenyl) -ethanone oxime is obtained as a white solid. The crude product is used in the next reaction step without further purification.
    9.3: 2,2,2-trifluoro-1- (2-methylphenyl) -ethanone oxime-O- (10-camphorylsulfonate)
    1.2 g (5.9 mmol) of 2,2,2-trifluoro-1- (2-methylphenyl) -ethanone oxime are dissolved in 30 ml of THF and cooled in an ice bath. 1.6 g (6.5 mmol) of 10-camphorylsulfonyl chloride is added to this solution, followed by the dropwise addition of 0.90 g (8.9 mmol) of triethylamine. The reaction mixture is stirred at 0 ° C. for 3 hours, then poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by flash chromatography on silica gel using ethyl acetate and hexane (1: 9) as eluent, and 1.2 g (2.9 mmol; 49%) of 2,2,2-trifluoro-1- (2). -Methylphenyl) -ethanone oxime-O- (10-camphorylsulfonate) is obtained as a colorless liquid. The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 0.92 (s, 3H), 1.12 (Z) /1.18 (E) (s, 3H), 1.38-1.50 (m, 1H), 1.55-1.75 (m, 1H), 1.90-2.18 (m , 3H), 2.28-2.53 (m, 5H), 3.25-3.38 (m, 1H), 3.84 (Z) /3.90 (E) (d, 1H), 7.15-7.46 (m, 4H). 1 H-NMR shows that the product is a mixture of Z and E isomers of 7: 3. Signals are temporarily designated as E- and Z-structures.
    Example 10 2,2,2-trifluoro-1- (2,4-dimethylphenyl) -ethanone oxime-O- (10-camphorylsulfonate)
    10.1: 2,2,2-trifluoro-1- (2,4-dimethylphenyl) -ethanone
    30.4 g (0.286 mol) of m-xylene and 34.9 g (0.286 mol) of 4-dimethylaminopyridine are mixed in 400 ml of CH 2 Cl 2 and cooled in an ice bath. To this solution is added 87.6 g (0.657 mol) of AlCl 3 , followed by the dropwise addition of 60 g (0.286 mol) of trifluoroacetic anhydride. The reaction mixture is stirred at rt overnight, poured into ice water and extracted with CH 2 Cl 2 . The organic phase is washed with water, aqueous NaHCO 3 and brine, dried over MgSO 4 and concentrated. The residue is distilled at 100 ° C./15 mm Hg and 12.6 g of crude product are obtained as a colorless liquid. This crude product is used in the next reaction step without further purification.
    10.2: 2,2,2-trifluoro-1- (2,4-dimethylphenyl) -ethanone oxime
    12.6 g (0.062 mol) of 2,2,2-trifluoro-1- (2,6-dimethylphenyl) -ethanone is dissolved in 30 ml of ethanol at 80 ° C. To this solution is added dropwise 4.6 g (0.066 mol) of hydroxylammonium chloride and 8.7 g (0.106 mol) of sodium acetate dissolved in 15 ml of water. The reaction mixture is refluxed overnight and a white precipitate is obtained. The mixture is poured into ice water and extracted with ethyl acetate. The organic phase is washed with water, aqueous NH 4 Cl and brine, dried over MgSO 4 , concentrated and 11.9 g of crude 2,2,2-trifluoro-1- (2,4-dimethylphenyl) -ethanone Oxime is obtained as a colorless liquid. The crude product is used in the next step without further purification.
    10.3: 2,2,2-trifluoro-1- (2,4-dimethylphenyl) -ethanone oxime-O- (10-camphorylsulfonate)
    2.0 g (9.2 mmol) of 2,2,2-trifluoro-1- (2,4-dimethylphenyl) -ethanone oxime are dissolved in 20 ml of THF and cooled in an ice bath. To this solution is added 2.5 g (10.1 mmol) of 10-camphorylsulfonyl chloride followed by the dropwise addition of 1.4 g (13.8 mmol) of triethylamine. The reaction mixture is stirred at 0 ° C. for 50 minutes, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by flash chromatography on silica gel using ethyl acetate and hexane (3: 7) as eluent, and 2.2 g (5.0 mmol; 54%) of 2,2,2-trifluoro-1- (2). , 4-dimethylphenyl) -ethanone oxime-O- (10-camphorylsulfonate) is obtained as a colorless liquid. The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 0.92 (s, 3H), 1.12 (Z) /1.18 (E) (s, 3H), 1.38-1.50 (m, 1H), 1.54-1.80 (m, 1H), 1.90-2.58 (m , 11H), 3.25-3.38 (m, 1 H), 3.83 (Z) /3.88 (E) (d, 1H), 7.03-7.28 (m, 3H). 1 H-NMR shows that the product is a mixture of 3: 2 Z and E isomers. Signals are temporarily designated as E- and Z-structures.
    Example 11: 2,2,2-trifluoro-1- (2,4-dimethylphenyl) -ethanone oxime-O- (1-naphthylsulfonate)
    2.0 g (9.2 mmol) of 2,2,2-trifluoro-1- (2,4-dimethylphenyl) -ethanone oxime (prepared as described in Example 10.2) are dissolved in 30 ml of THF, Cool in an ice bath. To this solution is added 2.3 g (10.1 mmol) of 1-naphthylsulfonyl chloride followed by the dropwise addition of 1.4 g (13.8 mmol) of triethylamine. The reaction mixture is stirred at 0 ° C. for 60 minutes, then poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by flash chromatography on silica gel using ethyl acetate and hexane (3: 7) as eluent, and 3.0 g (7.3 mmol; 80%) of 2,2,2-trifluoro-1- (2). , 4-dimethylphenyl) -ethanone oxime-O- (1-naphthylsulfonate) is obtained as a white solid (melting point, 85-124 ° C). The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 1.71 (E) /2.03 (Z) (s, 3H), 2.28 (E) /2.39 (Z) (s, 3H), 6.77-7.13 (m, 3H), 7.54-7.78 (m, 3H), 7.95-8.03 (m, 1 H), 8.15-8.23 (m, 1 H), 8.35-8.70 (m, 2H). 1 H-NMR shows that the product is a mixture of Z and E isomers of 7: 3. Signals are temporarily designated as E- and Z-structures.
    Example 12: 2,2,2-trifluoro-1- (2,4-dimethylphenyl) -ethanone oxime-O- (2-naphthylsulfonate)
    2.0 g (9.2 mmol) of 2,2,2-trifluoro-1- (2,4-dimethylphenyl) -ethanone oxime (prepared as described in Example 10.2) are dissolved in 30 ml of THF, Cool in an ice bath. To this solution is added 2.3 g (10.1 mmol) of 2-naphthylsulfonyl chloride followed by the dropwise addition of 1.4 g (13.8 mmol) of triethylamine. The reaction mixture is stirred at 0 ° C. for 60 minutes, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by flash chromatography on silica gel using ethyl acetate and hexane (3: 7) as eluent, and 2.1 g (5.3 mmol; 57%) of 2,2,2-trifluoro-1- (2). , 4-dimethylphenyl) -ethanone oxime-O- (2-naphthylsulfonate) is obtained as a colorless liquid. The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 2.05 (E) /2.10 (Z) (s, 3H), 2.31 (E) /2.35 (Z) (s, 3H), 6.92-7.13 (m, 3H), 7.61-7.77 (m, 2H), 7.88-8.08 (m, 4H), 8.61 (s, 1H). 1 H-NMR shows that the product is a mixture of Z and E isomers of 7: 3. Signals are temporarily designated as E- and Z-structures.
    Example 13: 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) -ethanone oxime-O- (10-camphorylsulfonate)
    13.1: 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) -ethanone
    50.0 g (0.416 mol) mesitylene and 50.8 g (0.416 mol) 4-dimethylaminopyridine are mixed in 600 ml of CH 2 Cl 2 and cooled in an ice bath. To this solution is added dropwise 87.4 g (0.416 mol) of trifluoroacetic anhydride, followed by addition of 128 g (0.957 mol) of AlCl 3 in portions. The reaction mixture is stirred at rt overnight, poured into ice water and extracted with CH 2 Cl 2 . The organic phase is washed with water, dried over MgSO 4 and concentrated. The residue is distilled at 100 ° C./1 mm Hg and 44.6 g of crude product are obtained as a colorless liquid. The crude product is used in the next step without further purification.
    13.2: 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) -ethanone oxime
    6.3 g (0.029 mol) of 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) -ethanone is dissolved in 30 ml of ethanol at 80 ° C. To this solution is added dropwise 2.0 g (0.029 mol) of hydroxylammonium chloride and 4.1 g (0.050 mol) of sodium acetate in 15 ml of water. The reaction mixture is refluxed overnight, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water, dried over MgSO 4 and concentrated. The residue was purified by recrystallization from 20 ml of hexane and 1.9 g of 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) -ethanone oxime in the form of a white solid (Melting point 119-125 ° C.).
    13.3: 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) -ethanone oxime-O- (10-camphorylsulfonate)
    1.8 g (7.8 mmol) of 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) -ethanone oxime are dissolved in 20 ml of THF and cooled in an ice bath. To this solution is added 2.2 g (8.6 mmol) of 10-camphorsulfonyl chloride followed by dropwise addition of 1.2 g (11.7 mmol) of triethylamine. The reaction mixture is stirred at 0 ° C. for 50 minutes, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by flash chromatography on silica gel using ethyl acetate and hexanes (1: 4) as eluent, and 3.4 g (7.6 mmol; 97%) of 2,2,2-trifluoro-1- (2). , 4,6-trimethylphenyl) -ethanone oxime-O- (10-camphorylsulfonate) is obtained as a colorless liquid. The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 0.92 (s, 3H), 1.14 (s, 3H), 1.40-1.49 (m, 1H), 1.65-1.75 (m, 1H), 1.93-2.47 (m, 14H), 3.35 (d, 1H), 3.84 (d, 1H), 7.12 (s, 2H).
    Example 14 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) -ethanone oxime-O- (1-naphthylsulfonate)
    2.0 g (8.7 mmol) of 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) -ethanone oxime (prepared as described in Example 13.2) was dissolved in 40 ml of THF. And cooled in an ice bath. To this solution is added 2.2 g (9.5 mmol) of 1-naphthylsulfonyl chloride and then 1.3 g (13.0 mmol) of triethylamine are added dropwise. The reaction mixture is stirred at 0 ° C. for 150 minutes, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by recrystallization from 5 ml of methanol and 1.5 g (3.6 mmol; 41%) of 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) -ethanone Oxime-O- (1-naphthylsulfonate) is obtained as a white solid (melting point 137-145 ° C.). The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 1.88-2.39 (m, 9H), 6.49-7.12 (m, 2H), 7.56-7.72 (m, 3H), 8.00 (t, 1H), 8.22 (d, 1H), 8.37-8.54 ( m, 2H).
    Example 15 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) -ethanone oxime-O- (2-naphthylsulfonate)
    2.0 g (8.7 mmol) of 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) -ethanone oxime (prepared as described in Example 13.2) was dissolved in 50 ml of THF. And cooled in an ice bath. To this solution is added 2.2 g (9.5 mmol) of 2-naphthylsulfonyl chloride followed by the dropwise addition of 1.4 g (14.3 mmol) of triethylamine. The reaction mixture is stirred at 0 ° C. for 210 minutes, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by recrystallization from hexane and ethyl acetate solution (9: 1) and 1.5 g (3.6 mmol; 41%) of 2,2,2-trifluoro-1- (2,4,6- Trimethylphenyl) -ethanone oxime-O- (2-naphthylsulfonate) is obtained as a white solid (melting point 106-113 ° C.). The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 2.21 (s, 3H), 2.30 (s, 6H), 7.01 (s, 2H), 7.63-7.76 (m, 2H), 7.96 (t, 2H), 8.03 (d, 2H), 8.62 (s, 1 H).
    Example 16: 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime-O-methylsulfonate
    16.1: 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone
    29.0 g (0.268 mol) of anisole and 32.8 g (0.268 mol) of 4-dimethylaminopyridine are mixed in 300 ml of CH 2 Cl 2 and cooled in an ice bath. To this solution is added 56.3 g (0.268 mol) of trifluoroacetic anhydride, followed by dropwise addition of 82.2 g (0.616 mol) of AlCl 3 in portions. The reaction mixture is stirred at rt overnight, poured into ice water and extracted with CH 2 Cl 2 . The organic phase is washed with water, dried over MgSO 4 and concentrated. The residue is purified by flash chromatography on silica gel using ethyl acetate and hexanes (5:95) as eluent to afford 37.8 g of the product as a brown liquid.
    16.2: 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime
    37.2 g (0.182 mol) of 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone are dissolved in 150 ml of ethanol at 80 ° C. To this solution is added dropwise 13.3 g (0.191 mol) of hydroxylammonium chloride and 25.4 g (0.309 mol) of sodium acetate in 75 ml of water. The reaction mixture is refluxed for 4 hours. The mixture is poured into ice water, the precipitate is filtered off and 30.0 g of 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime is obtained as a pale yellow solid. The crude product is used in the next reaction step without further purification.
    16.3: 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime-O- (methylsulfonate)
    6.5 g (30.0 mmol) of 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime are dissolved in 25 ml of THF and cooled in an ice bath. To this solution is added 3.8 g (33.0 mmol) methanesulfonyl chloride and then 4.6 g (45.0 mmol) triethylamine are added dropwise. The reaction mixture is stirred at 0 ° C. for 5 hours, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by recrystallization from 15 ml of ethanol and 5.9 g (20.0 mmol; 67%) of 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime-O- (Methylsulfonate) is obtained as a white solid (melting point 47-51 ° C.). The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). [pm]: 3.27 (s, 3H), 3.88 (s, 3H), 7.00 (d, 2H), 7.55 (d, 2H).
    Example 17 2,2,2-trifluoro-1- (4-methylthiophenyl) -ethanone oxime-O-methylsulfonate
    17.1: 2,2,2-trifluoro-1- (4-methylthiophenyl) -ethanone
    50.0 g (0.403 mol) of thioanisole and 49.2 g (0.403 mol) of 4-dimethylaminopyridine are mixed in 500 ml of CH 2 Cl 2 and cooled in an ice bath. To this solution is added dropwise 84.6 g (0.403 mol) trifluoroacetic anhydride, followed by addition of 123.0 g (0.926 mol) AlCl 3 in portions. The reaction mixture is stirred at rt overnight, poured into ice water and extracted with CH 2 Cl 2 . The organic phase is washed with water, dried over MgSO 4 , concentrated and 50.0 g of 2,2,2-trifluoro-1- (4-methylthiophenyl) -ethanone is obtained as a yellow solid. The crude product is used in the next reaction step without further purification.
    17.2: 2,2,2-trifluoro-1- (4-methylthiophenyl) -ethanone oxime
    49.3 g (0.224 mol) of 2,2,2-trifluoro-1- (4-methylthiophenyl) -ethanone are dissolved in 250 ml of ethanol at 80 ° C. To this solution is added dropwise 16.3 g (0.235 mol) of hydroxylammonium chloride and 31.2 g (0.381 mol) of sodium acetate dissolved in 125 ml of water. The reaction mixture is refluxed for 6.5 hours and poured into ice water. The precipitate is filtered to give 51.1 g of 2,2,2-trifluoro-1- (4-methylthiophenyl) -ethanone oxime as a yellow solid. The crude product is used in the next reaction step without further purification.
    17.3: 2,2,2-trifluoro-1- (4-methylthiophenyl) -ethanone oxime-O- (methylsulfonate)
    5.9 g (25.0 mmol) of 2,2,2-trifluoro-1- (4-methylthiophenyl) -ethanone oxime are dissolved in 30 ml of THF and cooled in an ice bath. To this solution is added 3.2 g (28.0 mmol) of methylsulfonyl chloride and then 3.8 g (38.0 mmol) of triethylamine are added dropwise. The reaction mixture is stirred at 0 ° C. for 5 hours, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by recrystallization from 30 ml of ethanol and 3.9 g (12.4 mmol; 50%) of 2,2,2-trifluoro-1- (4-methylthiophenyl) -ethanone oxime-O- (Methylsulfonate) is obtained as a pale yellow solid (melting point: 87-90 ° C.). The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 2.52 (s, 3H), 3.26 (s, 3H), 7.31 (d, 2H), 7.47 (d, 2H).
    Example 18 2,2,2-trifluoro-1- (3,4-dimethoxyphenyl) -ethanone oxime-O-methylsulfonate
    18.1: 2,2,2-trifluoro-1- (3,4-dimethoxyphenyl) -ethanone
    13.8 g (0.10 mol) of 1,2-dimethoxybenzene and 12.2 g (0.10 mol) of 4-dimethylaminopyridine are mixed in 75 ml of CH 2 Cl 2 and cooled in an ice bath. To this solution is added dropwise 21.0 g (0.10 mol) of trifluoroacetic anhydride, followed by addition of 32.0 g (0.24 mol) of AlCl 3 in portions. The reaction mixture is stirred at rt overnight, poured into ice water and extracted with CH 2 Cl 2 . The organic phase is washed with water, dried over MgSO 4 and concentrated. The residue is purified by flash chromatography on silica gel using ethyl acetate and hexanes (1: 9) as eluent and 2.9 g of the product are obtained as a white solid.
    18.2: 2,2,2-trifluoro-1- (3,4-dimethoxyphenyl) -ethanone oxime
    2.9 g (9.7 mmol) of 2,2,2-trifluoro-1- (3,4-dimethoxyphenyl) -ethanone are dissolved in 12 ml of ethanol at 80 ° C. To this solution is added dropwise 0.83 g (12.0 mmol) of hydroxylammonium chloride and 1.2 g (15.0 mmol) of sodium acetate dissolved in 6 ml of water. The reaction mixture is refluxed for 7.5 hours, poured into ice water and extracted with ether. The organic phase is washed with water and brine, dried over MgSO 4 , concentrated and 2.3 g of 2,2,2-trifluoro-1- (3,4-dimethoxyphenyl) -ethanone oxime are obtained. The crude product is used in the next reaction step without further purification.
    18.3: 2,2,2-trifluoro-1- (3,4-dimethoxyphenyl) -ethanone oxime-O-methylsulfonate
    2.3 g (9.0 mmol) of 2,2,2-trifluoro-1- (3,4-dimethoxyphenyl) -ethanone oxime are dissolved in 20 ml of THF and cooled in an ice bath. To this solution is added 1.2 g (10.0 mmol) of methylsulfonyl chloride and then 1.5 g (15.0 mmol) of triethylamine are added dropwise. The reaction mixture is stirred at 0 ° C. for 5 hours, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by recrystallization from 15 ml of ethanol and 2.2 g (6.7 mmol; 74%) of 2,2,2-trifluoro-1- (3,4-dimethoxyphenyl) -ethanone oxime- O- (methylsulfonate) is obtained as a white solid (melting point 105-107 ° C.). The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 3.27 (s, 3H), 3.91 (s, 3H), 3.95 (s, 3H), 6.96 (d, 1H), 7.05 (s, 1H), 7.20 (d, 1H).
    Example 19 2,2,3,3,4,4,4-heptafluoro-1-phenyl-butanone oxime-O- (10-camphorylsulfonate)
    19.1: 2,2,3,3,4,4,4-heptafluoro-1-phenyl-butanone oxime
    10 g (0.037 mol) of 2,2,3,3,4,4,4-heptafluoro-1-phenyl-butanone are dissolved in 30 ml of ethanol at 80 ° C. To this solution is added dropwise 2.6 g (0.038 mol) of hydroxylammonium chloride and 5.1 g (0.062 mol) of sodium acetate dissolved in 15 ml of water. The reaction mixture is refluxed for 6 hours. The mixture is poured into ice water and extracted with ethyl acetate. The organic phase is washed with brine, dried over MgSO 4 and concentrated. The residue is purified by recrystallization from 5 ml of hexane to give 4.7 g of 2,2,3,3,4,4,4-heptafluoro-1-phenyl-butanone oxime as a white solid (melting point 57-60 ° C.).
    19.2: 2,2,3,3,4,4,4-heptafluoro-1-phenyl-butanone oxime-O- (10-camphorylsulfonate)
    2.0 g (10.6 mmol) of 2,2,3,3,4,4,4-heptafluoro-1-phenyl-butanone oxime are dissolved in 40 ml of THF and cooled in an ice bath. To this solution is added 2.9 g (11.6 mmol) of 10-camphorylsulfonyl chloride followed by the dropwise addition of 1.6 g (16.0 mmol) of triethylamine. The reaction mixture is stirred at 0 ° C. for 4.5 h, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by flash chromatography on silica gel using ethyl acetate and hexane (1: 9) as eluent, and 2.3 g (4.6 mmol; 43%) of 2,2,3,3,4,4,4- Heptafluoro-1-phenyl-butanone oxime-O- (10-camphorylsulfonate) is obtained as a pale yellow liquid. The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 0.92 (s, 3H), 1.12 (Z) /1.18 (E) (s, 3H), 1.40-1.50 (m, 1H), 1.66-1.73 (m, 1H), 1.92-2.18 (m , 3H), 2.31-2.54 (m, 2H), 3.28 (Z) /3.33 (E) (d, 1H), 3.83 (Z) /3.93 (E) (d, 1H), 7.37-7.63 (m, 5H ). 1 H-NMR shows that the product is a mixture of 3: 2 Z and E isomers. Signals are temporarily designated as E- and Z-structures.
    Examples 20-36:
    The compounds of Examples 20-36 are obtained according to the method described in Example 1.2, using the corresponding vitreous. Structural and physical data are shown in Tables 1A-1C.

    Example 37
    R 1 is ego; R 2 is F; R 3 ' Compound of Formula 3
    The compound of Example 37 is prepared by reacting 2 mol of the corresponding oxime with 1 mol of the corresponding dichloride according to the method described in Example 1.2. The compound is a white solid with a melting point of 111-112 ° C. 1 H-NMR data [pm]: 7.00-7.13 (m, 8H), 7.20-7.28 (m, 2H), 7.38-7.48 (m, 8H), 7.87 (t, 1H), 8.36 (d, 2H), 8.63 (s, 1 H).
    Example 38:
    R 1 ' ego; R 2 is F; A compound of formula 2 wherein R 3 is -SO 2 CH 3
    The compound of Example 38 is prepared by reacting 1 mol of the corresponding bisoxime with 2 mol of the corresponding chloride according to the method described in Example 1.2. The compound is separated by chromatography using hexanes: ethyl acetate (5: 1) and is a pale yellow liquid. 1 H-NMR data [pm]: 3.25 / 3.27 (s, 6H), 4.43 (s, 4H), 7.02-7.08 (m, 4H), 7.53-7.62 (m, 4H).
    Example 39:
    R 1 ' ego; R 2 is F; Compound of Formula 2 wherein R 3 is -SO 2 C 3 H 7 .
    The compound of Example 39 is prepared as described in Example 38. The compound is separated by chromatography using hexanes: ethyl acetate (5: 1) and is an orange liquid. 1 H-NMR data [pm]: 1.12 (t, 6H), 1.88-2.02 (m, 4H), 3.34-3.43 (m, 4H), 4.43 (s, 4H), 7.00-7.07 (m, 4H) , 7.51-7.61 (m, 4H).
    Examples 40-74:
    The compounds of Examples 40-74 are obtained by the method described in Example 1.2, using the corresponding vitreous. Structural and physical data are listed in Tables 2A-2G.



    Example 75:
    R 1 is ego; R 2 is F; R 3 ' Compound of Formula 3
    The compound of Example 75 is prepared by reacting 2 mol of the corresponding oxime with 1 mol of the corresponding dichloride according to the method described in Example 1.2. The compound is purified by recrystallization from toluene and is a white solid with a melting point of 135 to 137 ° C. 1 H-NMR data, δ [pm]: 2.53 (s, 6H), 7.32 (d, 4H), 7.39 (d, 4H), 7.88 (t, 1H), 8.36 (d, 2H), 8.63 (s, 1H).
    Example 76:
    R 1 is ego; R 2 is F; R 3 ' Compound of Formula 3
    The compound of Example 76 is prepared by reacting 2 mol of the corresponding oxime with 1 mol of the corresponding dichloride according to the method described in Example 1.2. The compound is purified by recrystallization from ethanol and is a white solid with a melting point of 127 to 128 ° C. 1 H-NMR data, δ [pm]: 3.88 (s, 6H), 6.98 (d, 4H), 7.47 (d, 4H), 7.87 (t, 1H), 8.35 (d, 2H), 8.62 (s, 1H).
    Example 77:
    R 1 ' ego; R 2 is F; Compound of Formula 2 wherein R 3 is -SO 2 C 3 H 7 .
    The compound of Example 77 is prepared by reacting 1 mol of the corresponding bisoxime with 2 mol of the corresponding chloride according to the method described in Example 1.2. The compound is purified by recrystallization from methanol and is a white solid with a melting point of 84 to 86 ° C. 1 H-NMR data (CDCl 3 ); δ [pm]: 1.11 (t, 6H), 1.93 (m, 4H), 3.24 (s, 4H), 3.40 (t, 4H), 7.37 (d, 4H), 7.44 (d, 4H).
    Example 78: 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime-O- (1-propylsulfonate) (mixture of E-, Z-isomers)
    78.1: 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime (mixture of E-, Z-isomers)
    10 g (49.0 mmol) of 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone are dissolved in 100 ml of ethanol. To this solution is added 4.1 g (58.8 mmol) hydroxylammonium chloride and 11.9 ml (147 mmol) pyridine. The reaction mixture is refluxed for 4 hours and the solvent is distilled off on a rotary evaporator. The residue is poured into 50 ml of water and extracted with 100 ml and 50 ml of ethyl acetate. The organic phase is washed with aqueous potassium hydrogen sulfide solution, water and brine, dried over MgSO 4 and concentrated. The residue was purified by chromatography using methylene chloride, and 5.3 g of 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime was white solid having a melting point of 62 to 80 ° C. Obtained as The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 3.84 (s, 3H), 6.93 (E) /6.99 (Z) (d, 2H), 7.45 (E) /7.55 (Z) (d, 2H), 8.78 (br s, 1H). Signals are temporarily designated as E- and Z-structures. The spectrum shows that the compound is a mixture of E- and Z-isomers. The ratio of the mixture is evaluated as E: Z = 1: 1.
    78.2: 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime-O- (1-propylsulfonate) (mixture of E-, Z-isomers)
    3.7 g (17.0 mmol) of 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime (isomer mixture) are dissolved in 20 ml of THF and cooled in an ice bath. To this solution is added 2.7 g (18.7 mmol) of 1-propanesulfonyl chloride, followed by the dropwise addition of 3.6 ml (25.5 mmol) triethylamine. The reaction mixture is stirred at 0 ° C. for 1 h, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by chromatography using methylene chloride, and 5.4 g (16.5 mmol; 97%) of 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime-O- ( 1-propylsulfonate) is obtained as a pale yellow liquid. The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 1.11 (t, 3H), 1.88-2.02 (m, 2H), 3.34-3.43 (m, 2H), 3.88 (s, 3H), 6.95-7.03 (m, 2H), 7.52-7.58 ( m, 2H). The spectrum shows that the compound is a mixture of E- and Z-isomers.
    Example 79: 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime-O- (1-propylsulfonate) (monoisomer)
    79.1: 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime (monoisomer)
    118.5 g (0.58 mol) of 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone are dissolved in 470 ml of ethanol and heated at 80 ° C. To this solution is added 42.4 g (0.61 mol) of hydroxylammonium chloride and 80.9 g (0.99 mol) of sodium acetate dissolved in 240 ml of water. The reaction mixture is refluxed for 5 hours and the solvent is distilled off on a rotary evaporator. The residue is poured into 500 ml of water and a white solid precipitates. The solid was separated by filtration, washed with water, purified by recrystallization from toluene, and 73.1 g of 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime was white solid. Obtained as The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). [pm]: 3.84 (s, 3H), 6.99 (d, 2H), 7.55 (d, 2H), 9.11 (br s, 1H). The spectrum shows that the compound is temporarily a single isomer designated as Z-structure.
    79.2: 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime-O- (1-propylsulfonate) (monoisomer)
    12.0 g (54.8 mmol) of 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime (monoisomer) are dissolved in 100 ml of THF and cooled in an ice bath. To this solution is added 9.4 g (65.7 mmol) of 1-propanesulfonyl chloride followed by dropwise addition of 8.3 g (82.1 mmol) of triethylamine. The reaction mixture is stirred at 0 ° C. for 1 h, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by chromatography using methylene chloride, and 15.8 g (48.6 mmol; 89%) of 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime-O- ( 1-propylsulfonate) is obtained as a pale yellow liquid. The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 1.11 (t, 3H), 1.94 (m, 2H), 3.39 (t, 2H), 3.88 (s, 3H), 7.00 (d, 2H), 7.54 (d, 2H). The spectrum shows that the compound is temporarily a single isomer designated as Z-structure.
    Example 80 2,2,2-trifluoro-1- (4-phenoxyphenyl) -ethanone oxime-O- (1-propylsulfonate) (mixture of E-, Z-isomers)
    80.1: 2,2,2-trifluoro-1- (4-phenoxyphenyl) -ethanone oxime (mixture of E-, Z-isomers)
    122 g (0.46 mol) of 2,2,2-trifluoro-1- (4-phenoxyphenyl) -ethanone are dissolved in 370 ml of ethanol and heated at 80 ° C. To this solution is added dropwise 33.3 g (0.48 mol) of hydroxylammonium chloride and 63.7 g (0.78 mol) of sodium acetate dissolved in 190 ml of water. The reaction mixture is refluxed for 5.5 hours and poured into water. Pale yellow solid precipitates. The solid is filtered off, washed with water, added to hexanes and heated at 60 ° C. for 20 minutes. After cooling, the solid is separated, washed with hexane and 109 g of 2,2,2-trifluoro-1- (4-phenoxyphenyl) -ethanone oxime are obtained as a white solid. The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). [pm]: 7.00-7.10 (m, 4H), 7.18 (t, 1H), 7.39 (t, 2H), 7.55 (d, 2H), 9.35 (br s, 1H).
    80.2: 2,2,2-trifluoro-1- (4-phenoxyphenyl) -ethanone oxime-O- (1-propylsulfonate) (mixture of E-, Z-isomers)
    10 g (35.6 mmol) of 2,2,2-trifluoro-1- (4-phenoxyphenyl) -ethanone oxime (isomer mixture) are dissolved in 70 ml of THF and cooled in an ice bath. To this solution is added 7.2 g (50.2 mmol) of 1-propanesulfonyl chloride followed by the dropwise addition of 6.3 g (62.7 mmol) triethylamine. The reaction mixture is stirred at 0 ° C. for 1 h, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by chromatography using hexanes / ethyl acetate (5: 1) and 8.0 g (20.7 mmol; 58%) of 2,2,2-trifluoro-1- (4-phenoxyphenyl)- Ethanone oxime-O- (1-propylsulfonate) is obtained as a white solid with a melting point of 48 to 53 ° C. The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 1.07-1.18 (m, 3H), 1.92 (Z) /2.10 (E) (m, 2H), 3.40 (Z) /3.67 (E) (t, 2H), 7.00-7.12 (m, 4H), 7.15-7.28 (m, 1H), 7.34-7.45 (m, 2H), 7.51 (d, 2H). Signals are temporarily designated as E- and Z-structures. The spectrum shows that the compound is a mixture of E- and Z-isomers. The ratio of the mixture is evaluated as E: Z = 1: 5.
    Example 81: 2,2,2-trifluoro-1- (4-phenoxyphenyl) -ethanone oxime-O- (1-propylsulfonate) (monoisomer)
    81.1: 2,2,2-trifluoro-1- (4-phenoxyphenyl) -ethanone oxime (monoisomer)
    35 g (124 mmol) of 2,2,2-trifluoro-1- (4-phenoxyphenyl) -ethanone oxime (mixture of E- and Z-isomers) prepared by the method described in Example 80.1 Dissolve in 300 ml of methylene chloride. 1.1 ml of concentrated HCl is added to this solution and stirred at room temperature for 4.5 hours. The reaction mixture was washed with water and brine, dried over MgSO 4 , concentrated and 33.4 g of 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime (monoisomer) Obtained as a white solid. The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). [pm]: 7.00-7.12 (m, 4H), 7.19 (t, 1H), 7.39 (t, 2H), 7.57 (d, 2H), 8.95 (s, 1H).
    81.2: 2,2,2-trifluoro-1- (4-phenoxyphenyl) -ethanone oxime-O- (1-propylsulfonate) (monoisomer)
    10.0 g (35.6 mmol) of 2,2,2-trifluoro-1- (4-phenoxyphenyl) -ethanone oxime (monoisomer) are dissolved in 80 ml of THF and cooled in an ice bath. To this solution is added 5.6 g (39.1 mmol) of 1-propanesulfonyl chloride followed by the dropwise addition of 5.4 g (53.3 mmol) of triethylamine. The reaction mixture is stirred at 0 ° C. for 1 h, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by recrystallization from hexanes, and 12.6 g (32.5 mmol; 91%) of 2,2,2-trifluoro-1- (4-phenoxyphenyl) -ethanone oxime-O- (1 -Propylsulfonate) is obtained as a white solid with a melting point of 63 to 64 ° C. The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 1.11 (t, 3H), 1.92 (m, 2H), 3.40 (t, 2H), 7.05 (d, 2H), 7.11 (d, 2H), 7.23 (t, 1H), 7.42 (t , 2H), 7.51 (d, 2H). The spectrum shows that the compound is temporarily a single isomer designated as Z-structure.
    Example 82: 2,2,2-trifluoro-1- (4-dodecyloxyphenyl) -ethanone oxime-O- (1-propylsulfonate) (mixture of E-, Z-isomers)
    82.1: 2,2,2-trifluoro-1- (4-dodecyloxyphenyl) -ethanone oxime (mixture of E-, Z-isomers)
    32 g (89.3 mmol) of 2,2,2-trifluoro-1- (4-dodecyloxyphenyl) -ethanone are dissolved in 200 ml of ethanol. To this solution is added 7.4 g (107 mmol) hydroxylammonium chloride and 21.2 g (268 mmol) pyridine. The reaction mixture is refluxed for 1.5 hours and the solvent is distilled off on a rotary evaporator. The residue is poured into water and extracted with ethyl acetate. The organic phase is washed with aqueous potassium hydrogen sulfate solution, water and brine, dried over MgSO 4 and concentrated. The residue was purified by recrystallization from hexane / toluene and 8.4 g of 2,2,2-trifluoro-1- (4-dodecyloxyphenyl) -ethanone oxime having a melting point of 70 to 72 ° C. Obtained as a white solid. The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 0.89 (t, 3H), 1.20-1.40 (m, 16H), 1.40-1.50 (m, 2H), 1.79 (m, 2H), 3.86-4.03 (m, 2H), 6.93 (E) / 6.97 (Z) (d, 2H), 7.44 (E) / 7.53 (Z) (d, 2H), 8.59 (Z) / 8.61 (E) (br s, 1H). Signals are temporarily designated as E- and Z-structures. The spectrum shows that the compound is a mixture of E- and Z-isomers. The ratio of the mixture is evaluated as E: Z = 1: 4.
    82.2: 2,2,2-trifluoro-1- (4-dodecyloxyphenyl) -ethanone oxime-O- (1-propylsulfonate) (mixture of E- and Z-isomers)
    8.0 g (21.4 mmol) of 2,2,2-trifluoro-1- (4-dodecyloxyphenyl) -ethanone oxime (mixture of E- and Z-isomers) are dissolved in 50 ml of THF, Cool in an ice bath. To this solution is added 3.4 g (23.6 mmol) of 1-propanesulfonyl chloride followed by the dropwise addition of 3.3 g (32.1 mmol) of triethylamine. The reaction mixture is stirred at 0 ° C. for 1 h, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by recrystallization from methanol and 9.1 g (19.0 mmol; 89%) of 2,2,2-trifluoro-1- (4-dodecyloxyphenyl) -ethanone oxime-O- ( 1-propylsulfonate) is obtained as a white solid with a melting point of 40 to 41 ° C. The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 0.88 (t, 3H), 1.10 (t, 3H), 1.20-1.40 (m, 16H), 1.40-1.50 (m, 2H), 1.75-1.85 (m, 2H), 1.87-1.98 ( m, 2H), 3.32-3.42 (m, 2H), 4.00 (t, 2H), 6.93-7.00 (m, 2H), 7.48-7.57 (m, 2H). The spectrum shows that the compound is a mixture of E- and Z-isomers.
    Example 83 2,2,2-trifluoro-1- (4-dodecyloxyphenyl) -ethanone oxime-O- (1-propylsulfonate) (monoisomer)
    83.1: 2,2,2-trifluoro-1- (4-dodecyloxyphenyl) -ethanone oxime (monoisomer)
    15 g (41.8 mmol) of 2,2,2-trifluoro-1- (4-dodecyloxyphenyl) -ethanone are dissolved in 100 ml of ethanol. To this solution 3.5 g (50.2 mmol) hydroxylammonium chloride and 10.1 ml (125.4 mmol) pyridine are added. The reaction mixture is refluxed for 2 hours and the solvent is distilled off on a rotary evaporator. The residue is poured into 100 ml of water and extracted with 100 ml, followed by 50 ml of ethyl acetate. The organic phase is washed with aqueous potassium hydrogen sulfate solution, water and brine, dried over MgSO 4 and concentrated. The residue is dissolved in 100 ml of methylene chloride. To this solution is added 4.2 g of concentrated HCl. The reaction mixture is stirred overnight at room temperature and poured into water. After removal of the aqueous phase, the organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by recrystallization from hexane, and 9.7 g of 2,2,2-trifluoro-1- (4-dodecyloxyphenyl) -ethanone oxime was white solid having a melting point of 75 to 76 ° C. Obtained as The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 0.89 (t, 3H), 1.21-1.40 (m, 16H), 1.40-1.52 (m, 2H), 1.80 (m, 2H), 3.99 (t, 2H), 6.97 (d, 2H) , 7.53 (d, 2 H), 8.43 (s, 1 H). The spectrum shows that the compound is temporarily a single isomer designated as Z-structure. When sulfuric acid is used instead of HCl, a single isomer, 2,2,2-trifluoro-1- (4-dodecyloxyphenyl) -ethanone oxime, is also obtained.
    83.2: 2,2,2-trifluoro-1- (4-dodecyloxyphenyl) -ethanone oxime-O- (1-propylsulfonate) (monoisomer)
    7.0 g (18.7 mmol) of 2,2,2-trifluoro-1- (4-dodecyloxyphenyl) -ethanone oxime (monoisomer) are dissolved in 50 ml of THF and cooled in an ice bath. 2.9 g (20.6 mmol) of 1-propanesulfonyl chloride are added to this solution, followed by the dropwise addition of 3.9 ml (28.1 mmol) of triethylamine. The reaction mixture is stirred at 0 ° C. for 1 h, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by recrystallization from methanol and 7.6 g (15.9 mmol; 85%) of 2,2,2-trifluoro-1- (4-dodecyloxyphenyl) -ethanone oxime-O- ( 1-propylsulfonate) is obtained as a white solid with a melting point of 42-44 ° C. The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 0.88 (t, 3H), 1.10 (t, 3H), 1.20-1.40 (m, 16H), 1.40-1.50 (m, 2H), 1.80 (m, 2H), 1.94 (m, 2H) , 3.48 (t, 2H), 4.00 (t, 2H), 6.97 (d, 2H), 7.53 (d, 2H). The spectrum shows that the compound is temporarily a single isomer designated as Z-structure.
    Example 84 2,2,2-trifluoro-1- (4-hexadecyloxyphenyl) -ethanone oxime-O- (1-propylsulfonate) (mixture of E-, Z-isomers)
    84.1: 2,2,2-trifluoro-1- (4-hexadecyloxyphenyl) -ethanone oxime (mixture of E-, Z-isomers)
    27 g (65.1 mmol) of 2,2,2-trifluoro-1- (4-hexadecyloxyphenyl) -ethanone are dissolved in 100 ml of ethanol. To this solution is added 4.5 g (65.1 mmol) hydroxylammonium chloride and 12.9 g (163 mmol) pyridine. The reaction mixture is refluxed for 4 hours and the solvent is distilled off on a rotary evaporator. The residue is poured into water and extracted with ethyl acetate. The organic phase is washed with aqueous potassium hydrogen sulfate solution, water and brine, dried over MgSO 4 and concentrated. The residue was purified by recrystallization from hexane / toluene and 13.5 g of 2,2,2-trifluoro-1- (4-hexadecyloxyphenyl) -ethanone oxime having a melting point of 76 to 80 ° C Obtained as a beige solid. The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 0.88 (t, 3H), 1.20-1.40 (m, 24H), 1.40-1.50 (m, 2H), 1.75-1.84 (m, 2H), 3.96-4.02 (m, 2H), 6.89 ( E) /6.95 (Z) (d, 2H), 7.43 (E) /7.52 (Z) (d, 2H), 8.28 (Z) /8.43 (E) (br s, 1H). Signals are temporarily designated as E- and Z-structures. The spectrum shows that the compound is a mixture of E- and Z-isomers. The ratio of the mixture is evaluated as E: Z = 7: 3.
    84.2: 2,2,2-trifluoro-1- (4-hexadecyloxyphenyl) -ethanone oxime-O- (1-propylsulfonate) (mixture of E-, Z-isomers)
    8.0 g (18.6 mmol) of 2,2,2-trifluoro-1- (4-hexadecyloxyphenyl) -ethanone oxime (mixture of E-, Z-isomers) are dissolved in 50 ml of THF, Cool in an ice bath. To this solution is added 2.9 g (20.5 mmol) of 1-propanesulfonyl chloride and then 2.8 g (27.9 mmol) of triethylamine are added dropwise. The reaction mixture is stirred at 0 ° C. for 1 h, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by recrystallization from methanol and 8.9 g (16.6 mmol; 89%) of 2,2,2-trifluoro-1- (4-hexadecyloxyphenyl) -ethanone oxime-O- ( 1-propylsulfonate) is obtained as a white solid with a melting point of 56 to 57 ° C. The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 0.88 (t, 3H), 1.12 (t, 3H), 1.18-1.40 (m, 24H), 1.40-1.50 (m, 2H), 1.76-1.85 (m, 2H), 1.88-2.02 ( m, 2H), 3.32-3.44 (m, 2H), 4.02 (t, 2H), 6.93-7.00 (m, 2H), 7.48-7.56 (m, 2H). The spectrum shows that the compound is a mixture of E- and Z-isomers.
    Example 85: 2,2,2-trifluoro-1- (4-hexadecyloxyphenyl) -ethanone oxime-O- (1-propylsulfonate) (monoisomer)
    85.1: 2,2,2-trifluoro-1- (4-hexadecyloxyphenyl) -ethanone oxime (monoisomer)
    5.3 g (12.3 mmol) of 2,2,2-trifluoro-1- (4-hexadecyloxyphenyl) -ethanone oxime (mixture of E- and Z-isomers) prepared by the method described in Example 84.1 Is dissolved in 100 ml of methylene chloride. 1.0 ml of concentrated HCl is added to this solution and stirred overnight at room temperature. The reaction mixture is washed with water and brine, dried over MgSO 4 , concentrated and 5.3 g of 2,2,2-trifluoro-1- (4-hexadecyloxyphenyl) -ethanone oxime (monoisomer) Obtained as a white solid with a melting point of 84 to 85 ° C. The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 0.88 (t, 3H), 1.20-1.40 (m, 24H), 1.40-1.50 (m, 2H), 1.80 (m, 2H), 4.00 (t, 2H), 6.95 (d, 2H) , 7.52 (d, 2H), 8.06 (s, 1H). The spectrum shows that the compound is temporarily a single isomer designated as Z-structure.
    85.2: 2,2,2-trifluoro-1- (4-hexadecyloxyphenyl) -ethanone oxime-O- (1-propylsulfonate) (monoisomer)
    5.2 g (12.2 mmol) of 2,2,2-trifluoro-1- (4-hexadecyloxyphenyl) -ethanone oxime (monoisomer) are dissolved in 50 ml of THF and cooled in an ice bath. To this solution is added 1.9 g (13.3 mmol) of 1-propanesulfonyl chloride followed by the dropwise addition of 1.84 g (18.2 mmol) of triethylamine. The reaction mixture is stirred at 0 ° C. for 1 h, poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue was purified by recrystallization from methanol and 5.8 g (10.8 mmol; 89%) of 2,2,2-trifluoro-1- (4-hexadecyloxyphenyl) -ethanone oxime-O- ( 1-propylsulfonate) is obtained as a white solid with a melting point of 59 to 60 ° C. The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 0.88 (t, 3H), 1.12 (t, 3H), 1.23-1.41 (m, 24H), 1.41-1.50 (m, 2H), 1.80 (m, 2H), 1.93 (m, 2H) , 3.40 (t, 2H), 4.02 (t, 2H), 6.97 (d, 2H), 7.53 (d, 2H). The spectrum shows that the compound is temporarily a single isomer designated as Z-structure.
    Example 86:
    (Mixture of E-, Z-isomers) CJ39-0188
    R 1 ' ego; R 2 is F; Compound of Formula 2 wherein R 3 is -SO 2 C 3 H 7 .
    86.1:
    The compound of Example 86.1 is prepared by reacting 1 mol of 1.3-diphenoxypropane with 2 mol of 4-dimethylaminopyridine, 2 mol of trifluoroacetic anhydride and 5 mol of AlCl 3 according to the method described in Example 7.1. The crude product is purified by recrystallization from toluene.
    86.2:
    (Mixture of E-, Z-isomers)
    18.0 g (42.8 mmol) of the compound of Example 86.1 are dissolved in 100 ml of ethanol. To this solution is added 6.0 g (85.7 mmol) hydroxylammonium chloride and 16.9 g (214 mmol) pyridine. The reaction mixture is refluxed for 4 hours and the solvent is distilled off on a rotary evaporator. The residue is poured into water and extracted with ethyl acetate. The organic phase is washed with aqueous potassium hydrogen sulfate solution, water and brine, dried over MgSO 4 and concentrated. The residue is purified by recrystallization from toluene and 16.1 g of the compound of Example 86.2 are obtained as a white solid. The structure is confirmed by the 1 H-NMR spectrum (DMSO-d 6 ). [pm]: 2.22-2.34 (m, 2H), 4.22-4.32 (m, 4H), 7.06-7.17 (m, 4H), 7.47 / 7.52 (d, 4H). The spectrum shows that the compound is a mixture of E- and Z-isomers.
    86.3:
    (Mixture of E-, Z-isomers)
    8.0 g (17.8 mmol) of the compound of Example 86.2 (a mixture of E-, Z-isomers) are dissolved in 80 ml of THF and cooled in an ice bath. To this solution is added 5.6 g (39.1 mmol) of 1-propanesulfonyl chloride followed by the dropwise addition of 5.4 g (53.3 mmol) of triethylamine. The reaction mixture is stirred for 2 h at 0 ° C., poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue is purified by chromatography using hexanes / ethyl acetate (2: 1) and 10.7 g (16.1 mmol; 91%) of the compound of Example 86.3 are obtained as a pale yellow solid having a melting point of 80 to 84 ° C. The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 1.12 (t, 6H), 1.97 (m, 4H), 2.36 (m, 2H), 3.35-3.45 (m, 4H), 4.25 (t, 4H), 6.98-7.06 (m, 4H) , 7.54 / 7.58 (d, 4H). The spectrum shows that the compound is a mixture of E- and Z-isomers.
    Example 87
    (Single isomer)
    87.1:
    (Single isomer)
    21.0 g (50.0 mmol) of the compound of Example 86.1 are dissolved in 150 ml of ethanol. To this solution is added 8.4 g (120 mmol) hydroxylammonium chloride and 23.8 g (300 mmol) pyridine. The reaction mixture is refluxed for 1.5 hours and the solvent is distilled off on a rotary evaporator. The residue is poured into water and extracted with ethyl acetate. The organic phase is washed with aqueous potassium hydrogen sulfate solution, water and brine, dried over MgSO 4 and concentrated. The residue is dissolved in 150 ml of ethyl acetate. 0.43 ml of concentrated HCl is added to this solution and stirred at room temperature for 2 hours. The reaction mixture is washed with water and brine, dried over MgSO 4 and concentrated. The residue is purified by recrystallization from toluene and 21.4 g of the compound of Example 87.1 are obtained as a white solid. The structure is confirmed by the 1 H-NMR spectrum (DMSO-d 6 ). δ [pm]: 2.43 (m, 2H), 4.42 (t, 4H), 7.30 (d, 4H), 7.70 (d, 4H). The spectrum shows that the compound is temporarily a single isomer designated as Z-structure.
    87.2:
    (Single isomer)
    8.0 g (17.8 mmol) of the compound of Example 87.1 (monoisomer) are dissolved in 80 ml of THF and cooled in an ice bath. To this solution is added 5.6 g (39.1 mmol) of 1-propanesulfonyl chloride followed by the dropwise addition of 5.4 g (53.3 mmol) of triethylamine. The reaction mixture is stirred for 2 h at 0 ° C., poured into ice water and extracted with ethyl acetate. The organic phase is washed with water and brine, dried over MgSO 4 and concentrated. The residue is purified by recrystallization from methanol and 9.1 g (13.7 mmol; 77%) of the compound of Example 87.2 are obtained as a white solid with a melting point of 60-62 ° C. The structure is confirmed by 1 H-NMR spectrum (CDCl 3 ). δ [pm]: 1.12 (t, 6H), 1.97 (m, 4H), 2.36 (m, 2H), 3.39 (t, 4H), 4.25 (t, 4H), 7.02 (d, 4H), 7.53 (d , 4H). The spectrum shows that the compound is a single isomer temporarily designated as Z, Z-structure.
    Example 88:
    Chemically amplified positive resist formulations are prepared by mixing the following ingredients:
    Resin binder (copolymer of 22 mol% styrene, 69 mol% p-hydroxy-styrene and 9 mol% t-butyl acrylate, Mw = 9850; RTM Maruzen MARUKA LYNCUR PHS / STY / TBA, Maruzen oil Company (made in Maruzen Oil Company, Japan) 100.0 parts
    Leveling agent (FC-430, 3M company) 0.4 parts
    Propylene glycol methyl ether acetate (PGMEA) (manufactured by Tokyo Kasei, Japan) 400.0 parts
    Part 4.0 of the photoacid generator to be tested.
    The resist formulation was spin-coated with hexamethyl dimethylsilane-treated silicon wafer at 6500 rpm for 60 seconds and (soft baking) on a hotplate at 140 ° C. for 90 seconds to obtain a film of 800 nm thick. Narrow band interference filters were formed using high pressure mercury lamps (manufactured by Ushio), UXM-501MD, and mask aligner Canon PLA-521. After exposure to a deep ultraviolet exposure wavelength of 254 nm through a multidensity quartz mask, the exposure is baked for 90 seconds on a hotplate at 140 ° C. and then developed. Exposure intensity is measured with a Unimeter UIT-150 (manufactured by Ushio Corporation). The dose to clear (E 0 ) [the dose sufficient to completely remove the resist film with a 90 second immersion in 2.38% aqueous tetramethyl ammonium hydroxide developer] is determined from the measured opposite curve (characteristic curve). R. Dammel, Diazonaphthoquinone-based Resists, SPIE Tutorial Text Series Vol. TT 11, Optical Engineering Press, p. 10-11 (1993). The less dose required, the more sensitive the resist formulation is. The results are shown in Table 3 and demonstrate that the composition is suitable for positive photoresist.
    Example CompoundDose to Clear (E 0 ) (mJ / cm 2 ) 20.18 30.18 50.10 60.23 131.14 160.19 170.24 200.16 210.16 260.25 270.15 290.07
    Example 89:
    Chemically amplified negative resist formulations are prepared by mixing the following ingredients:
    Resin binder (poly (p-hydroxystyrene), Mw = 11900; RTM VP-8000, manufactured by Nisso, Japan) 100.0 parts
    10.0 parts of melamine urea resin [N, N'-dimethoxymethylurea, RTM MX-290, Sangwa Chemical Co., LTD.] As a crosslinking agent.
    Leveling agent ( RTM FC-430, manufactured by 3M) 0.5 part
    7.7 parts of photoacid generator (PAG) to be tested
    Propylene Glycol Methyl Ether Acetate (PGMEA) (manufactured by Tokyo Kasei Co., Japan) 500.0 parts
    The resist formulation is spin coated with a hexamethyl dimethylsilane-treated silicon wafer to a thickness of 800 nm for 60 seconds at 6000 rpm. Softbaking on a vacuum hotplate at 110 ° C. for 60 seconds yields a tack-free resist film. The resist film was exposed to a 254 nm exposure wavelength through a narrow band filter and a multi-density quartz mask using a high pressure mercury lamp (manufactured by Ushio Corporation), UXM-501MD and a mask regulator Canon PLA-521 to expose the gel dose (D 0 ). Membrane is obtained similarly to Example 88 except that the membrane is baked for 60 seconds at 110 ° C. after exposure and for 60 seconds before immersion in 2.38% aqueous tetramethyl ammonium hydroxide]. It is determined by the amount of irradiation sufficient to leave the thin film of the resist crosslinked to the substrate after development. The opposite curves for both positive and negative resists (characteristic curves) include doses to clear (for positive resists) and gel doses (for negative resists (see E. Reichmanis and LF Thompson, ACS Symp. Ser. 412, Polymers in Microlithography, p. 4-5, American Chemical Society, Washington, DC 1989). The negative resist sensitivity obtained is shown in Table 4.
    Example 90
    Chemically amplified positive resist formulations are prepared by mixing the following ingredients:
    100.00 parts of the same resin binder as described in Example 88
    Leveling agent (FC-430, 3M company) 0.48 parts
    Propylene Glycol Methyl Ether Acetate (PGMEA) (manufactured by Tokyo Kasei Co., Japan) 475.00 parts
    Part 4.0 of the photoacid generator to be tested
    The resist formulation was spin-coated with hexamethyl dimethylsilane-treated silicon wafer at 3000 rpm for 45 seconds, and swept-baked on a hotplate at 140 ° C. for 90 seconds to obtain a film having a thickness of 800 nm. The resist film was then exposed to deep ultraviolet radiation at a wavelength of 254 nm through a narrow band filter and a multi-density quartz mask using a high pressure mercury lamp (manufactured by Ushio Corporation), UXM-501MD, and Canon PLA-521, a mask regulator. The sample is then post-exposure baked on a hotplate at 140 ° C. for 90 seconds and developed. Exposure intensity is measured by the unit UIT-150 (manufactured by Ushio Corporation). The dose to clear (E 0 ) [the dose sufficient to completely remove the resist film by 60 seconds immersion in 1.79% aqueous tetramethyl ammonium hydroxide developer] is determined from the measured opposite curve. The smaller the dose required, the more sensitive the resist formulation is. The results are shown in Table 5, demonstrating that the composition is suitable for the production of positive photoresists.
    Example CompoundDose until clear (E 0 ) [mJ / cm 2 ] 401.79 411.63 421.32 431.50 440.91 454.61 460.72 474.16 481.63 490.99 501.22 511.22 520.99 530.56 540.69 550.69 561.17 575.01 582.02 591.47 613.07 621.51 632.77 642.66 651.57 662.90 671.11 691.33 702.20 724.25 750.89 761.30 791.21 801.54 811.55 835.00 857.27 871.73
    Example 91:
    Decomposition point of photo-lactate generator compound (Td) in the presence of the same amount (in weight units) of poly (4-hydroxystyrene) [Mw = 5100, trade name: Maruzene MARUKA LYNCUR PHMC (manufactured by Maruzen Oil Company, Tokyo, Japan)] ) Is measured by DSC (differential scanning calorimetry) analysis. The higher the value, the more thermally stable the photolatonic acid compound tested. The results are summarized in Tables 6a and 6b.
    Example CompoundTd (℃) One〉 200 2〉 200 3180 5183 6〉 200 8〉 200 13197 15173 16186 17192 18175 20196 21176 22180 23219 25197 27188 40174 41170 42〉 200 43185 44186 45174 46198 47〉 200 48〉 200 49172 50193 51〉 200 52〉 200 53186 54190 55184 56〉 200 57〉 200 58〉 200 59191 61〉 200 62193 63〉 200
    Example CompoundTd (℃) 64〉 200 65〉 200 66186 67187 69173 70175 72〉 200 75175 76175 79190 80188 81〉 200 83〉 200 85197 87188
    Example 92:
    In the presence of the same amount (in weight units) of poly (4-hydroxystyrene), the decomposition point (Td) of the photo lactate generator compound is measured as described in Example 91. The results are shown in Table 7.
    Example CompoundTd (℃) 78 (isomer mixture)116, 185 1)79 (78 single isomers)190 80 (isomer mixture)185,〉 200 1)81 (80 single isomers)〉 200 82 (isomer mixture)151,〉 200 1)83 (82 single isomers)〉 200 84 (isomer mixture)150, 197 1)85 (84 single isomers)197 86 (isomer mixture)140, 188 1)87 (86 single isomers)188 1) Two peaks appear in the DSC measurement. The numerical value is calculated from the starting point of the decomposition.
    Chemically amplified photoresist compositions comprising the oxime derivatives of the present invention are thermally stable at high baking temperatures during processing and provide high luminous flux.
    权利要求:
    Claims (11)
    [1" claim-type="Currently amended] (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) A chemically amplified photoresist composition comprising as a photosensitive acid donor at least one compound of Formula 1, Formula 2 or Formula 3.
    Formula 1

    Formula 2

    Formula 3

    In the above formula,
    R 1 is hydrogen; Unsubstituted C 1 -C 12 alkyl; C 1 -C 12 alkyl substituted with C 3 -C 30 cycloalkyl; R 1 is C 3 -C 30 cycloalkyl, C 1 -C 8 haloalkyl, C 2 -C 12 alkenyl, C 4 -C 8 cycloalkenyl, C 6 -C 12 bicycloalkenyl, camphoryl; Unsubstituted or one or more radicals C 1 -C 12 -alkyl, C 1 -C 4 haloalkyl, phenyl-C 1 -C 3 -alkyl, halogen, phenyl, OR 4 , NR 5 R 6 , SR 7 , SOR 7 And / or phenyl substituted by SO 2 R 7 , optionally the substituents OR 4 , SR 7 and NR 5 R 6 together with further substituents on the phenyl ring or one carbon atom of the phenyl ring radical R 4 , R 5 , R To form a 5- or 6-membered ring via 6 and / or R 7 ; R 1 is naphthyl, anthracyl or phenanthryl unsubstituted or substituted by C 1 -C 6 alkyl, phenyl, OR 4 , NR 5 R 6 , SR 7 , SOR 7 and / or SO 2 R 7 , Optionally the substituents OR 4 , SR 7 and NR 5 R 6 together with further substituents on the naphthyl, anthracyl or phenanthryl ring or the radical R 4 , R 5, R together with one carbon atom of the naphthyl, anthracyl or phenanthryl ring To form a 5- or 6-membered ring via 6 and / or R 7 ; Or R 1 is a heteroaryl radical unsubstituted or substituted with C 1 -C 6 alkyl, phenyl, OR 4 , NR 5 R 6 , SR 7 , SOR 7 and / or SO 2 R 7 , optionally substituted with OR 4 , SR 7 and NR 5 R 6 form a 5- or 6-membered ring via the radicals R 4 , R 5 , R 6 and / or R 7 together with one carbon atom of an additional substituent or heteroaryl ring on the heteroaryl ring To; Wherein all radicals R 1 except hydrogen may be optionally substituted by a group having an —OC— bond or —O—Si— bond which decomposes upon the action of an acid;
    R ' 1 is unsubstituted or substituted with C 1 -C 12 alkyl phenylene, naphthylene, , Diphenylene or oxydiphenylene, or R ' 1 is C 1 -C 12 alkylene or Is;
    A is -O-, -S-, -NR 4- , -O (CO)-, -S (CO)-, -NR 4 (CO)-, -SO-, -SO 2 -or -OSO 2- ego;
    A 1 is C 1 -C 12 alkylene or C 2 -C 12 alkylene blocked by one or more -O-;
    R 2 is halogen or C 1 -C 10 haloalkyl;
    R 3 is C 1 -C 18 alkylsulfonyl, C 1 -C 10 haloalkylsulfonyl, camphorylsulfonyl, phenyl-C 1 -C 3 alkylsulfonyl, C 3 -C 12 cycloalkylsulfonyl, phenylsulfonyl , Naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl, wherein the radical C 3 -C 12 cycloalkylsulfonyl, phenyl-C 1 -C 3 alkylsulfonyl, phenylsulfonyl, naphthylsulfonyl, anthracylsulfonyl And the group cycloalkyl, phenyl, naphthyl, anthracyl and phenanthryl of phenanthrylsulfonyl are unsubstituted or substituted with one or more halogen, C 1 -C 4 haloalkyl, CN, NO 2 , C 1 -C 16 alkyl, phenyl , Substituted by C 1 -C 4 alkylthio, OR 4 , COOR 7 , C 1 -C 4 alkyl- (OC) O—, R 7 OSO 2 — and / or —NR 5 R 6 ; Or R 3 is C 2 -C 6 haloalkanoyl, halobenzoyl, or a group or ego;
    Y 1 , Y 2 and Y 3 are each independently O or S;
    R ' 3 is phenylenedisulfonyl, naphthylenedisulfonyl, unsubstituted or substituted with C 1 -C 12 alkyl, , Diphenylenedisulfonyl or oxydiphenylenedisulfonyl; Or R ' 3 is C 2 -C 12 alkylenedisulfonyl;
    X is halogen;
    R 4 is hydrogen, phenyl, unsubstituted or phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR 5 R 6 , C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 1 -C 18 alkyl substituted with C 2 -C 6 alkanoyl; R 4 is blocked with one or more —O— and is unsubstituted, or is phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbon C 2 -C 18 alkyl substituted with aryl, NR 5 R 6 , C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) -sulfonyl and / or C 2 -C 6 alkanoyl; R 4 is unsubstituted or is phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR 5 R 6 , C 1 C 2 -C 18 alkanoyl substituted with —C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 -C 6 alkanoyl; R 4 is unsubstituted or is phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR 5 R 6 , C 1 C 1 -C 18 alkylsulfonyl substituted with —C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 -C 6 alkanoyl; Or R 4 is phenylsulfonyl, or (4-methylphenyl) sulfonyl;
    R 5 and R 6 are each independently hydrogen or unsubstituted, OH, C 1 -C 4 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl , C 1 -C 18 alkyl substituted with phenylamino, phenylaminocarbonyl, C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methyl-phenyl) sulfonyl and / or C 1 -C 6 alkanoyl Or; R 5 and R 6 are blocked with one or more —O— and are unsubstituted or substituted with OH, C 1 -C 4 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthio C 2 -C 18 alkyl substituted with carbonyl, phenylamino, phenylaminocarbonyl, C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 1 -C 6 alkanoyl Or; R 5 and R 6 are unsubstituted or are phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, phenylamino, phenyl C 2 -C 18 alkanoyl substituted with aminocarbonyl, C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 -C 6 alkanoyl; R 5 and R 6 are unsubstituted or are phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, phenylamino, phenyl C 1 -C 18 alkylsulfonyl substituted with aminocarbonyl, C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 -C 6 alkanoyl; R 5 and R 6 are phenyl, benzoyl, phenylsulfonyl, (4-methylphenyl) sulfonyl, 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 blocked with -O- or -NR 4- ;
    R 7 is hydrogen, phenyl, unsubstituted or phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR 5 R 6 , C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 1 -C 18 alkyl substituted with C 2 -C 6 alkanoyl; R 7 is blocked with one or more —O— and is unsubstituted, or is phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbon N 2 , C 2 -C 18 alkyl substituted with NR 5 R 6 , C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 -C 6 alkanoyl; R 7 is unsubstituted or is phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR 5 R 6 , C 1 C 2 -C 18 alkanoyl substituted with —C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 -C 6 alkanoyl; R 7 is unsubstituted or is phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR 5 R 6 , C 1 C 1 -C 18 alkylsulfonyl substituted with —C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 -C 6 alkanoyl; Or R 7 is phenylsulfonyl or (4-methylphenyl) sulfonyl;
    R 8 , R 9 and R 10 are independently of each other unsubstituted or substituted C 1 -C 6 alkyl substituted with halogen; R 8 , R 9 and R 10 are unsubstituted or phenyl substituted with C 1 -C 4 alkyl or halogen; Or R 9 and R 10 together are 1,2-phenylene or C 2 -C 6 -alkylene unsubstituted or substituted with C 1 -C 4 alkyl or halogen.
    [2" claim-type="Currently amended] The compound of claim 1, wherein R 1 is unsubstituted or one or more radicals C 1 -C 12 -alkyl, phenyl-C 1 -C 3 -alkyl, halogen, OR 4 , NR 5 R 6 , SR 7 , SOR 7 and / Or phenyl substituted with SO 2 R 7 , optionally the substituent OR 4 forms a 6-membered ring via the radical R 4 ; Or R 1 is naphthyl or thienyl;
    R ' 1 Is;
    A is -O- or -S-;
    A 1 is C 1 -C 12 alkylene;
    R 2 is halogen or C 1 -C 10 haloalkyl;
    R 3 is C 1 -C 18 alkylsulfonyl, camphorylsulfonyl, phenyl-C 1 -C 3 -alkylsulfonyl, phenylsulfonyl, naphthylsulfonyl, wherein the phenyl group of the radical phenylsulfonyl is unsubstituted or , Is substituted by C 1 -C 16 alkyl or OR 4 ;
    R ' 3 is phenylenedisulfonyl;
    X is fluoro;
    R 4 is phenyl, C 1 -C 18 alkyl unsubstituted or substituted by C 2 -C 12 -alkoxycarbonyl; Or R 4 is C 2 -C 18 alkyl blocked with one or more —O— and substituted by phenyl;
    R 5 and R 6 are C 1 -C 18 alkyl;
    A chemically amplified photoresist composition comprising a compound of Formula 1, Formula 2 and Formula 3 wherein R 7 is phenyl or C 1 -C 18 alkyl.
    [3" claim-type="Currently amended] The method of claim 1,
    (a1) one or more polymers having acid-labile groups that decompose in the presence of an acid to increase solubility in aqueous alkaline developer solution and / or
    (a2) at least one monomer or oligomer degradation inhibitor having an acid-labile group which is decomposed in the presence of an acid to increase solubility in an aqueous alkaline developer solution and / or
    (a3) at least one alkali-soluble monomer, oligomeric or polymeric compound, and
    (b) A chemically amplified positive photoresist composition comprising at least one compound of Formula 1, Formula 2 or Formula 3 as a photosensitive acid donor.
    [4" claim-type="Currently amended] The method of claim 1,
    (a4) alkali-soluble resins as binders;
    (a5) a component undergoing a crosslinking reaction on its own and / or together with a binder when catalyzed by an acid and
    (b) A chemically amplified negative photoresist composition comprising at least one formula (I), formula (II) or formula (3) as photosensitive acid donor.
    [5" claim-type="Currently amended] The method according to claim 1, further comprising components (a) and (b) or components (a1), (a2), (a3) and (b), or components (a4), (a5) and (b). A chemically amplified photoresist composition comprising an additive (c), an additional photosensitive acid donor compound (b1), other photoinitiator (d), and / or a photosensitive agent (e).
    [6" claim-type="Currently amended] (1) applying a composition according to any one of claims 1 to 5 on a substrate;
    (2) baking the composition of step (1) at a temperature of 60 ° C. to 160 ° C. after application;
    (3) image-wise irradiation using light rays in the wavelength range of 150 nm to 1500 nm;
    (4) optionally baking the composition after exposure at a temperature between 60 ° C. and 160 ° C. and
    (5) A method of producing a photoresist by developing using a solvent or an aqueous alkaline developer.
    [7" claim-type="Currently amended] Compounds of Formula 1b, 2b or 3b.
    Formula 1b

    Formula 2b

    Formula 3b

    In the above formula,
    R ″ 1 is unsubstituted or one or more C 1 -C 12 alkyl, phenyl-C 1 -C 3 -alkyl, C 1 -C 4 haloalkyl, halogen, phenyl, OR 4 , NR 5 R 6 , SR 7 , Phenyl substituted with SOR 7 and / or SO 2 R 7 , and optionally the substituents OR 4 , SR 7 and NR 5 R 5 are further substituents on the phenyl ring via the radicals R 4 , R 5 , R 6 and / or R 7 Or together with one carbon atom of the phenyl ring form a 5- or 6-membered ring; R ″ 1 is unsubstituted or C 1 -C 6 alkyl, phenyl, OR 4 , NR 5 R 6 , SR 7 , SOR 7 And / or naphthyl, anthracyl or phenanthryl substituted by SO 2 R 7 and optionally the substituents OR 4 , SR 7 and NR 5 R 5 are via the radicals R 4 , R 5 , R 6 and / or R 7 Form a 5- or 6-membered ring with additional substituents on the phenyl ring or one carbon atom of the naphthyl, anthracyl or phenanthryl ring or one carbon atom of the naphthyl, anthracyl or phenanthryl ring; Or R ″ 1 is a heteroaryl radical unsubstituted or substituted with C 1 -C 6 alkyl, phenyl, OR 4 , NR 5 R 6 , SR 7 , SOR 7 and / or SO 2 R 7 , optionally substituted OR 4 , SR 7 and NR 5 R 6 may be substituted via a radical R 4 , R 5 , R 6 and / or R 7 together with a further substituent on the heteroaryl ring or with one carbon atom of the heteroaryl ring to form a 5- or 6-membered ring; Form;
    R ''' 1 is unsubstituted or substituted with C 1 -C 12 alkyl, phenylene, naphthylene, , Diphenylene or oxydiphenylene; Or R ''' 1 ego;
    A is -O-, -S-, -NR 4- , -O (CO)-, -S (CO)-, -NR 4 (CO)-, -SO-, -SO 2 -or -OSO 2- Is;
    A 1 is C 1 -C 12 alkylene or C 2 -C 12 alkylene blocked with one or more -O-;
    R ″ 3 is C 1 -C 16 alkylsulfonyl, phenyl-C 1 -C 3 alkylsulfonyl, camphorylsulfonyl, naphthylsulfonyl, trimethylphenylsulfonyl, or one or more C 2 -C 16 alkyl, C 1- Phenylsulfonyl substituted with C 4 alkoxy, C 1 -C 4 haloalkyl and / or halogen;
    R ' 3 is phenylenedisulfonyl, naphthylenedisulfonyl, unsubstituted or substituted with C 1 -C 12 alkyl, , Diphenylenedisulfonyl or oxydiphenylenedisulfonyl; Or R ' 3 is C 2 -C 12 alkylenedisulfonyl;
    R 4 is hydrogen, phenyl, unsubstituted or phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR 5 R 6 , C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 1 -C 12 alkyl substituted by C 2 -C 6 alkanoyl; R 4 is interrupted by one or more —O— and is unsubstituted or substituted with phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthio carbonyl, NR 5 R 6, C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 -C 6 alkanoyl substituted with a C 2 -C 12 alkyl, or by; R 4 is unsubstituted or is phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR 5 R 6 , C 1 -C 12- alkyl-sulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 a C 2 -C 12 alkanoyl which is substituted by -C 6 alkanoyl, or; R 4 is unsubstituted or is phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR 5 R 6 , C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 -C 6 alkynyl optionally substituted by a C 1 -C 12 alkanoyl or alkylsulfonyl; Or R 4 is phenylsulfonyl or (4-methylphenyl) sulfonyl;
    R 5 and R 6 are each independently hydrogen or unsubstituted, OH, C 1 -C 4 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl , phenylamino, phenyl-aminocarbonyl, C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methyl-phenyl) sulfonyl and / or C 1 -C 6 alkanoyl of C 1 -C 12 alkyl substituted with Or; R 5 and R 6 are interrupted by one or more —O—, unsubstituted, OH, C 1 -C 4 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenyl thiocarbonyl, phenylamino, phenyl-aminocarbonyl, C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 1 -C 6 alkanoyl substituted by a C 2 -C 12 alkyl; R 5 and R 6 are unsubstituted or phenyl, OH, C 1 -C 12 -alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, phenylamino, C 2 -C 12 alkanoyl substituted by phenylaminocarbonyl, C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) -sulfonyl and / or C 2 -C 6 alkanoyl; R 5 and R 6 are unsubstituted or are phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, phenylamino, phenyl Aminocarbonyl, C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) -sulfonyl and / or C 1 -C 12 alkylsulfonyl substituted by C 2 -C 6 alkanoyl; R 5 and R 6 are phenylsulfonyl or (4-methylphenyl) sulfonyl; R 5 and R 6 are phenyl, benzoyl, 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 optionally blocked with -O- or -NR 4- ;
    R 7 is hydrogen, phenyl, unsubstituted or phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR 5 R 6 , C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 1 -C 12 alkyl substituted with C 2 -C 6 alkanoyl; R 7 is blocked with one or more —O— and is unsubstituted, or is phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbon N 2 , C 2 -C 12 alkyl substituted with NR 5 R 6 , C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) -sulfonyl and / or C 2 -C 6 alkanoyl; R 7 is unsubstituted or is phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR 5 R 6 , C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 -C 6 alkynyl optionally substituted with a C 2 -C 12 alkanoyl or alkanoyl; R 7 is unsubstituted or is phenyl, OH, C 1 -C 12 alkoxy, C 2 -C 12 alkoxycarbonyl, phenoxy, phenoxycarbonyl, phenylthio, phenylthiocarbonyl, NR 5 R 6 , C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl) sulfonyl and / or C 2 -C 6 alkynyl optionally substituted with a C 1 -C 12 alkanoyl or alkylsulfonyl; Or R 7 is phenylsulfonyl or (4-methylphenyl) sulfonyl; Provided that when R " 1 is 4-methylphenyl or 4-octylphenyl, R" 3 is not methanesulfonyl.
    [8" claim-type="Currently amended] (1) treating an isomeric mixture of the corresponding oxime compound (10) or (11), obtained by a conventional method, with an acid; and
    (2) An oxime ester compound of formula 1, 2 or 3 according to claim 1, by reacting the single isomeric oxime compound thus prepared with the corresponding acid halides (15), (16) and (17). Or a process for the specific preparation of thermally stable isomers of the oxime ester compounds of formula 1b, 2b or 3b.
    10

    (11)

    R 3 Cl (15)

    R " 3 Cl (16)

    Cl-R ' 3 -Cl (17)
    In the chemicals,
    R 1 , R 2 , R 3 and R ' 3 , and X are as defined in claim 1,
    R ″ 3 is as defined in claim 10.
    [9" claim-type="Currently amended] (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) A photosensitive acid donor comprising at least one compound of formula 1b, formula 2b or formula 3b according to claim 7.
    [10" claim-type="Currently amended] A compound of formula (Ib), (2b) and / or (3b) according to claim 7 is added to a compound capable of crosslinking upon the action of an acid and irradiated in a phase-wise or over the entire region using light with a wavelength of 150 to 1500 nm. A crosslinking method of a compound that can crosslink upon the action of an acid, including.
    [11" claim-type="Currently amended] 11. The method of claim 10, wherein the surface coating, printing ink, printing plate, dental composition, color filter, resist or image-recording material, or phase-recording material for holographic image recording.
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    同族专利:
    公开号 | 公开日
    NL1019981A1|2002-04-11|
    AT410262B|2003-03-25|
    ITMI20000662A1|2001-10-01|
    ATA5422000A|2002-07-15|
    NL1014545A1|2000-10-03|
    AU766803B2|2003-10-23|
    SE0001090D0|2000-03-28|
    NL1014545C2|2002-02-26|
    NL1019981C2|2002-10-03|
    ES2168953B1|2003-10-16|
    AU2420000A|2000-10-05|
    CH694663A5|2005-05-31|
    SE0001090L|2000-10-01|
    KR100700901B1|2007-03-29|
    ES2168953A1|2002-06-16|
    ITMI20000662D0|2000-03-30|
    CA2302875A1|2000-09-30|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1999-03-31|Priority to EP99810273.5
    1999-03-31|Priority to EP99810273
    1999-04-07|Priority to EP99810287.5
    1999-04-07|Priority to EP99810287
    1999-08-30|Priority to EP99810779.1
    1999-08-30|Priority to EP99810779
    2000-03-30|Application filed by 에프. 아. 프라저, 에른스트 알테르 (에. 알테르), 한스 페터 비틀린 (하. 페. 비틀린), 피. 랍 보프, 브이. 스펜글러, 페. 아에글러, 시바 스페셜티 케미칼스 홀딩 인크.
    2000-10-25|Publication of KR20000063080A
    2003-03-11|First worldwide family litigation filed
    2007-03-29|Application granted
    2007-03-29|Publication of KR100700901B1
    优先权:
    申请号 | 申请日 | 专利标题
    EP99810273.5|1999-03-31|
    EP99810273|1999-03-31|
    EP99810287.5|1999-04-07|
    EP99810287|1999-04-07|
    EP99810779.1|1999-08-30|
    EP99810779|1999-08-30|
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