Oxime ester photoinitiators

• US 7,759,043 B2
• Filed: 08/08/2005
• Issued: 07/20/2010
• Est. Priority Date: 08/18/2004
• Status: Expired due to Fees

• Current Assignee: CIBA Specialty Chemicals
• Original Assignee: CIBA Specialty Chemicals
• Inventors: Kunimoto, Kazuhiko, Ohwa, Masaki, Tanabe, Junichi, Oka, Hidetaka, Kura, Hisatoshi
• Primary Examiner(s): Kelly; Cynthia H
• Assistant Examiner(s): Johnson; Connie P
• Application Number:
  US11/660,346
• Publication Number:
  US 20080096115A1
• Time in Patent Office: 1,807 Days
• Field of Search: 430/270.1, 546/1, 548/400, 548/416, 548/427
• US Class Current: 430/270.1
• CPC Class Codes: C07D 209/86 with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
• CPC Class Codes: C07D 413/10 linked by a carbon chain containing aromatic rings
• CPC Class Codes: C09B 55/003 with the -C=N- group attached to an heteroring
• CPC Class Codes: G03F 7/031 Organic compounds not covered by group G03F7/029

Abstract

Compounds of the formula (I), wherein R₁, R₂ and R₁₀ independently of one another are C₁-C₂₀alkyl, phenyl, C₁-C₁₂alkylphenyl or phenyl-C₁-C₆alkyl; R₃ and R₄ independently of one another are hydrogen, C₁-C₂₀alkyl, NR₆R₇ or SR₈, provided that at least one of R₃ or R₄ is NR₆R₇ or SR₈; R₅ is hydrogen or C₁-C₂₀alkyl; R₆ and R₇ independently of one another are C₁-C₂₀alkyl, or R₆ and R₇ together with the N-atom to which they are attached form a 5 or 6 membered ring, which optionally is interrupted by O, S or NR₉ and which optionally additionally is substituted by one or more C₁-C₄alkyl; R₈ is phenyl, biphenylyl, naphthyl, anthryl or phenanthryl, all of which optionally are substituted by one or more C₁-C₄alkyl; and R₉ is hydrogen, C₁-C₂₀alkyl, C₂-C₄hydroxyalkyl or phenyl; exhibit an unexpectedly good performance in photopolymerization reactions.

Claims

1. A compound of the formula I

2. A compound of the formula I according to claim 1, wherein

R₁ and R₂ independently of one another are C₁-C₁₂alkyl;

R₃ is NR₆R₇ or SR₈;

R₄ is hydrogen;

R₅ is hydrogen;

R₆ and R₇ independently of one another are C₁-C₁₂alkyl, or R₆ and R₇ together with the N-atom to which they are attached form a 5 or 6 membered ring, which optionally is interrupted by O, and which optionally additionally is substituted by one or more C₁-C₄alkyl;

R₈ is phenyl; and

R₁₀ is methyl.

3. A photopolymerizable composition comprising

(a) at least one ethylenically unsaturated photopolymerizable compound and

(b) as photoinitiator, at least one compound of the formula I according to claim 1.

4. A photopolymerizable composition according to claim 3 comprising in addition to the photoinitiator (b) at least one further photoinitiator (c) and/or other additives (d).

5. A photopolymerizable composition according to claim 3, comprising 0.05 to 25% by weight of the photoinitiator (b).

6. A photopolymerizable composition according to claim 3 comprising a further additive (d) comprising a photosensitizer.

7. A photopolymerizable composition according to claim 3 additionally comprising a binder polymer (e).

8. A process for the photopolymerization of compounds containing ethylenically unsaturated double bonds, which comprises irradiating a composition according to claim 3 with electromagnetic radiation in the range from 150 to 600 nm, or with electron beam or with X-rays.

9. A process for the preparation of a compound of the formula I according to claim 1 by reacting an oxime compound of formula II

10. A process according to claim 8 for producing pigmented and nonpigmented paints and varnishes, powder coatings, printing inks, printing plates, adhesives, dental compositions, gel coats, photoresists for electronics like electroplating resists, etch resists, both liquid and dry films, solder resists, resists to manufacture color filters for a variety of display applications or to generate structures in the manufacturing processes of plasma-display panels, electroluminescence displays and LCD, spacers for LCD, for holographic data storage (HDS), as composition for encapsulating electrical and electronic components, for producing magnetic recording materials, micromechanical parts, waveguides, optical switches, plating masks, etch masks, colour proofing systems, glass fibre cable coatings, screen printing stencils, and as image recording material, for holographic recordings, microelectronic circuits, decolorizing materials, decolorizing materials for image recording materials, for image recording materials using microcapsules, as a photoresist material for a UV and visible laser direct imaging system, and as a photoresist material used for forming dielectric layers in a sequential build-up layer of a printed circuit board.

11. Coated substrate which is coated on at least one surface with a composition according to claim 3.

12. Process for the photographic production of relief images, in which a coated substrate according to claim 11 is subjected to imagewise exposure and then the unexposed portions are removed with a developer.

14. A photopolymerizable composition according to claim 4, comprising 0.05 to 25% by weight of the photoinitiators (b) and (c), based on the composition.

15. A photopolymerizable composition according to claim 6, wherein further additive (d) comprises a photosensitizer compound selected from the group consisting of benzophenone and its derivatives, thioxanthone and its derivatives, anthraquinone and its derivatives, and coumarin and its derivatives.

16. A photopolymerizable composition according to claim 4 wherein further additive (d) comprises a photosensitizer.

17. A photopolymerizable composition according to claim 16, wherein further additive (d) comprises a photosensitizer compound selected from the group consisting of benzophenone and its derivatives, thioxanthone and its derivatives, anthraquinone and its derivatives, and coumarin and its derivatives.

18. A photopolymerizable composition according to claim 7, wherein the binder polymer (e) is a copolymer of methacrylate and methacrylic acid.

19. A photopolymerizable composition according to claim 4 additionally comprising a binder polymer (e).

13. A compound of the formula II