Oxime sulfonates and the use thereof as latent sulfonic acids

{
  "publication_number": "US6004724A",
  "country": "US",
  "kind": "A",
  "title": "Oxime sulfonates and the use thereof as latent sulfonic acids",
  "abstract": "New oximsulfonate compounds of the formulae I or II, ##STR1## wherein m is 0 or 1; x is 1 or 2; R 1 is, for example phenyl, which is unsubstituted or substituted or R 1 is a heteroaryl radical that is unsubstituted or substituted, or, if m is 0, R 1 additionally is C 2 -C 6 alkoxycarbonyl, phenoxycarbonyl or CN; R' 1 is for example C 2 -C 12 alkylene, phenylene; R 2 has for example one of the meanings of R 1; n is 1 or 2; R 3 is for example C 1 -C 18 alkyl, R' 3 when x is 1, has one of the meanings given for R 3, or R' 3 in the formula IV and when x is 2 in the formula 1, is for example C 2 -C 12 alkylene, phenylene; R 4 and R 5 are independently of each other for example hydrogen, halogen, C 1 -C 6 alkyl; R 6 is for example hydrogen, phenyl; R 7 and R 8 are independently of each other for example hydrogen or C 1 -C 12 -alkyl; R 9 is for example C 1 -C 12 alkyl; A is S, O, NR 6, or a group of formula A1, A2, A3 or A4 ##STR2## R 10 and R 11 independently of each other have one of the meanings given for R 4; R 12, R 13, R 14 and R 15 independently of one another are for example hydrogen, C 1 -C 4 alkyl; Z is CR 11 or N; Z 1 is --CH 2 --, S, O or NR 6, are useful as latent sulfonic acids, especially in photoresist applications.",
  "claims": [
    "1. A compounds of the formulae I or II ##STR75## m is 0 or 1; x is 1 or 2 R 1 is phenyl, which is unsubstituted or substituted by one or more of the radicals C 1 -C 12 alkyl, C 1 -C 4 haloalkyl, halogen, phenyl, OR 6, NR 7 R 8, SR 9 or --S-phenyl, it being possible for the substituents OR 6, SR 9 and NR 7 R 8 to form 5- or 6-membered rings, via the radicals R 6, R 7, R 8 or R 9, with further substituents on the phenyl ring or with one of the carbon atoms of the phenyl ring, or R 1 is naphthyl, anthracyl or phenanthryl, the radicals naphthyl, anthracyl and phenanthryl being unsubstituted or substituted by C 1 -C 6 alkyl, phenyl, OR 6, NR 7 R 8, SR 9 or --S-phenyl, it being possible for the substituents OR 6, SR 9 and NR 7 R 8 to form 5- or 6-membered rings, via the radicals R 6, R 7, R 8 or R 9 with further substituents on the naphthyl, anthracyl or phenanthryl ring or with one of the carbon atoms of the naphthyl, anthracyl or phenanthryl ring, or R 1 is a heteroaryl radical that is unsubstituted or substituted by C 1 -C 6 alkyl, phenyl, OR 6, NR 7 R 8, SR 9 or --S-phenyl, it being possible for the substituents OR 6, SR 9 and NR 7 R 8 to form 5- or 6-membered rings, via the radicals R 6, R 7, R 8 or R 9 with further substituents on the heteroaryl ring or with one of the carbon atoms of the heteroaryl ring, or, if m is 0, R 1 additionally is C 2 -C 6 alkoxycarbonyl, phenoxycarbonyl or CN; or R 1 is H or C 1 -C 12 alkyl, with the proviso that R 2 is not simultaneously H or alkyl; R' 1 is C 2 -C 12 alkylene, phenylene, naphthylene, ##STR76## diphenylene or oxydiphenylene, the radicals phenylene, naphthylene, ##STR77## diphenylene and oxydiphenylene being unsubstituted or substituted by C 1 -C 12 alkyl; R 2 has one of the meanings of R 1 or is unsubstituted or CN-substituted phenyl, C 2 -C 6 -alkanoyl, benzoyl that is unsubstituted or substituted by C 1 -C 6 alkyl, phenyl, OR 6, SR 9, NR 7 R 8 or --S-phenyl, or R 2 is phenoxycarbonyl, NO 2, C 1 -C 4 haloalkyl, S(O) n C 1 -C 6 alkyl, unsubstituted or C 1 -C 12 alkyl-substituted S(O)n--C 6 -C 12 aryl, SO 2 O--C 1 -C 6 alkyl, SO 2 O--C 6 -C 10 aryl, diphenyl-phosphinoyl or NHCONH 2, or R 1 and R 2 together with the CO group, form a 5- or 6-membered ring that is unsubstituted or substituted by C 1 -C 6 alkyl, phenyl, OR 6, SR 9, NR 7 R 8 or --S-phenyl, and said ring may additionally be interrupted by O,S, NR 7 or by CO, and to which ring one or more benzo radicals may be fused; n is 1 or 2; or R 3 is C 1 -C 18 alkyl, phenyl-C 1 -C 3 alkyl, camphoryl, C 1 -C 10 haloalkyl, phenyl, naphthyl, anthracyl or phenanthryl, the radicals phenyl, naphthyl, anthracyl and phenanthryl being unsubstituted or substituted by one or more of the radicals halogen, C 1 -C 4 haloalkyl, CN, NO 2, C 1 -C 16 alkyl, phenyl, OR 6, COOR 9, --OCO--C 1 -C 4 alkyl, SO 2 OR 9 or NR 7 R 8; R' 3 when x is 1, has one of the meanings given for R 3, and when x is 2, R' 3 is C 2 -C 12 alkylene, phenylene, naphthylene, ##STR78## diphenylene or oxydiphenylene, the radicals phenylene, naphthylene, ##STR79## diphenylene and oxydiphenylene being unsubstituted or substituted by C 1 -C 12 alkyl; R 4 and R 5 are independently of each other hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 4 haloalkyl, CN, NO 2, C 2 -C 6 alkanoyl, benzoyl, phenyl, --S-phenyl, OR 6, SR 9, NR 7 R 8, C 2 -C 6 alkoxycarbonyl, phenoxycarbonyl, S(O) n C 1 -C 6 alkyl, unsubstituted or C 1 -C 12 alkyl-substituted S(O) n --C 6 -C 12 aryl, SO 2 O--C 1 -C 6 alkyl, SO 2 O--C 6 -C 10 aryl or NHCONH 2, or R 4 and R 5 together are --C(R 12)═C(R 13)--C(R 14)═C(R 15)--; R 6 is hydrogen, phenyl, C 1 -C 12 alkyl which is unsubstituted or substituted by phenyl, OH, C 1 -C 12 alkoxy, C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl or by C 2 -C 6 alkanoyl and said C 1 -C 12 alkyl may additionally be interrupted by --O--; R 7 and R 8 are independently of each other hydrogen or C 1 -C 12 alkyl which is unsubstituted or substituted by OH, C 1 -C 4 alkoxy, C 1 -C 12 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl or C 1 -C 6 alkanoyl and said C 1 -C 12 alkyl may additionally be interrupted by --O--, or R 7 and R 8 are phenyl, C 2 -C 6 alkanoyl, benzoyl, C 1 -C 6 alkylsulfonyl, phenylsulfonyl, (4-methylphenyl)sulfonyl, naphthylsulfonyl, anthracylsulfonyl or phenanthrylsulfonyl, or R 7 and R 8, together with the nitrogen atom to which they are bonded, form a 5-, 6- or 7-membered ring which may be interrupted by --O-- or by --NR 6 --; R 9 is C 1 -C 12 alkyl which is unsubstituted or substituted by OH or C 1 -C 4 alkoxy and said C 1 -C 12 alkyl may additionally be interrupted by --O--; A is S, O, NR 6, or a group of formula A1, A2, A3 or A4 ##STR80## R 10 and R 11 independently of each other have one of the meanings given for R 4, or R 10 and R 11 together are --CO--NR 6 CO--, or R 10 and R 11 together are --C(R 12)═C(R 13)--C(R 14)═C(R 15)--; R 12, R 13, R 14 and R 15 independently of one another are hydrogen, C 1 -C 4 alkyl, halogen, phenyl, OR 6, SR 9, NR 7 R 8, --S-phenyl, C 2 -C 6 alkoxycarbonyl, phenoxycarbonyl, CN, NO 2, C 1 -C 4 haloalkyl, S(O) n C 1 -C 6 alkyl, unsubstituted or C 1 -C 12 alkyl-substituted S(O)n--C 6 -C 12 aryl, SO 2 O--C 1 -C 6 alkyl, SO 2 O--C 6 -C 10 aryl or NHCONH 2; Z is CR 11 or N; Z 1 is --CH 2 --, S, O or NR 6.",
    "2. A compound according to claim 1 of the formula I or II, wherein m is 0; x is 1; R 1 is unsubstituted phenyl or phenyl substituted by C 1 -C 6 alkyl, phenyl, OR 6, SR 9, --S-phenyl, halogen or NR 7 R 8, it being possible for the substituents OR 6, and NR 7 R 8 to form 5- or 6-membered rings, via the radicals R 6, R 7 or R 8, with further substituents of the phenyl ring or with one of the carbon atoms of the phenyl ring; R' 1 is phenylene, naphthylene, ##STR81## diphenylene or oxydiphenylene, the radicals phenylene, naphthylene, ##STR82## diphenylene and oxydiphenylene being unsubstituted or substituted by C 1 -C 12 alkyl.",
    "3. Compounds according to claim 1, of the formula Ia ##STR83## R 1, R 2, R 3, R 4, R 5 and A are as defined in claim 1.",
    "4. Compounds according to claim 3, of formula Ia, wherein R 1 is unsubstituted phenyl or phenyl substituted once or twice by C 1 -C 4 alkyl, OR 6 or halogen or R, is naphthyl or thienyl; R 2 is CN; R 3 is C 1 -C 16 alkyl, camphoryl or unsubstituted phenyl or phenyl 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; R 4 and R 5 independently of each other are hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, NR 7 R 8 or phenyl or R 4 and R 5 together are --C(R 12)═C(R 13)--C(R 14)═C(R 15)--; R 6 is C 1 -C 4 alkyl or C 1 14 C 4 alkylsulfonyl; R 7 and R 8 independently of one another are hydrogen or phenyl; A is --S--, NR 6 or a group of the formula A 1 ##STR84## Z is CR 11 or N; and R 10, R 11, R 12, R 13, R 14 and R 15 are hydrogen.",
    "5. A composition comprising a) at least one compound that can be crosslinked under the action of an acid and/or b) at least one compound the solubility of which is altered under the action of an acid and c) as latent acid photoinitiator, at least one compound of the formulae I or II according to claim 1.",
    "6. A composition according to claim 5, which comprises in addition to component c) further photoinitiators, sensitisers or additives.",
    "7. A method of crosslinking compounds that can be crosslinked under the action of an acid, which method comprises adding as a photosensitive acid a compound of formula I or II according to claim 1 to the above-mentioned compounds and irradiating imagewise or over the whole area with light having a wavelength of 180-1500 nm.",
    "8. A photoresist based on oximesulfonates as photosensitive acid donors, the photoresist comprising as oximesulfonate a compound of formula I or II according to claim 1.",
    "9. A photoresist according to claim 8, which photoresist is a negative resist.",
    "10. A photoresist according to claim 8, which photoresist is a positive resist.",
    "11. A photoresist according to claim 8, which photoresist is a chemically amplified resist.",
    "12. A photoresist according to claim 8, comprising polymers that are transparent down to the wavelength region of 180 nm.",
    "13. A method for the preparation of surface coatings, printing inks, printing plates, dental compositions, colour filters, resist materials and as image-recording material, or image-recording material for recording holographic images, which comprises irradiating a composition according to claim 5 with light having a wavelength of 180-1500 nm."
  ],
  "description_excerpt": "The invention relates to new oximesulfonate compounds, photopolymerisable compositions comprising said compounds and to the use of the compounds as latent sulfonic acid photoinitiators, which can be activated by irradiation with light.\n\nIn U.S. Pat. No. 4,540,598 surface-coating compositions based on photosensitive oxime sulfonates and customary acid-curable resins are disclosed. In EP 571330 the use of α-(4-toluene-sulfonyloxyimino)-4-methoxybenzyl cyanide and α(4-toluene-sulfonyloxyimino)-3-thienylmethyl cyanide as latent acid donors in positive and negative photoresists for wavelengths of 340-390 nm, especially those in the radiation region of the mercury i line (365 nm) is described. In GB 2306958 the use of oxime-sulfonates as latent acid donors in positive and negative photoresists for wavelengths between 180 and 600 nm, especially those in the radiation region beyond 390 nm is reported.\n\nIn the art, a need still exists, especially for reactive non-ionic latent acid donors that are thermally and chemically stable and that, after being activated by light, can be used as catalysts for a variety of acid-catalysed reactions, such as polycondensation reactions, acid-catalysed depolymerisation reactions, acid-catalysed electrophilic substitution reactions or the acid-catalysed removal of protecting groups. There is also a need for compounds that when irradiated with light are converted into acids and are capable of acting as solubility inhibitors in resist formulations. Furthermore there is a need for photolatent acids which can be bleached upon irradiation.",
  "cpc": [
    "C07D 207/44",
    "C07C 309/65",
    "C07C 309/66",
    "C07C 309/73",
    "C07C 323/63",
    "C07C 381/00",
    "C07D 213/90",
    "C07D 333/44",
    "G03F 7/0045",
    "Y10S 430/114",
    "Y10S 430/117",
    "Y10S 430/12",
    "Y10S 430/122"
  ],
  "ipc": [
    "C07C 309/65",
    "C07C 309/66",
    "C07C 309/73",
    "C07C 323/63",
    "C07C 381/00",
    "C07D 207/44",
    "C07D 213/90",
    "C07D 333/34",
    "C07D 333/36",
    "C07D 333/44",
    "G03F 7/004"
  ],
  "assignees": [
    "Ciba Specialty Chemicals Corp"
  ],
  "inventors": [
    "Hitoshi Yamato",
    "Hartmut Bleier",
    "Jean-Luc Birbaum",
    "Martin Kunz",
    "Kurt Dietliker",
    "Christoph De Leo",
    "Toshikage Asakura"
  ],
  "filing_date": "1998-06-25",
  "publication_date": "1999-12-21",
  "grant_date": "1999-12-21",
  "priority_date": "1997-07-01",
  "application_number": "US-10467698-A",
  "family_id": "8230280",
  "cited_by_count": 213,
  "citations": [
    "US4540598A",
    "US4736055A",
    "EP0571330A1",
    "GB2306958A"
  ]
}