Oxime ester photoinitiators

• US 9,365,515 B2
• Filed: 12/03/2012
• Issued: 06/14/2016
• Est. Priority Date: 12/07/2011
• Status: Active Grant

• Current Assignee: BASF SE
• Original Assignee: BASF SE
• Inventors: Nishimae, Yuichi, Kura, Hisatoshi, Kunimoto, Kazuhiko, Yamagami, Ryuhei, Tanaka, Keita
• Primary Examiner(s): McPherson, John A
• Application Number:
  US14/361,113
• Publication Number:
  US 20140334027A1
• Time in Patent Office: 1,289 Days
• Field of Search: 430/7, 430/325, 430/281.1, 430/287.1, 522/14, 522/36, 522/39
• US Class Current: 1/1
• CPC Class Codes: C07D 209/80 [b, c]- or [b, d]-condensed
• 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 403/12 linked by a chain containing hetero atoms as chain links
• CPC Class Codes: C07D 409/04 directly linked by a ring-member-to-ring-member bond
• CPC Class Codes: C07D 409/14 containing three or more hetero rings
• CPC Class Codes: C08F 2/50 with sensitising agents
• CPC Class Codes: G02B 5/201 in the form of arrays
• CPC Class Codes: G03F 7/0007 Filters, e.g. additive colour filters; Components for display devices
• CPC Class Codes: G03F 7/20 Exposure; Apparatus therefor photographic printing apparatus for making copies G03B27/00

Abstract

Oxime ester compounds of formula (I), wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, and R₁₀ independently of each other are hydrogen, C₁-C₂₀alkyl, (A), COR₁₄, NO₂, or OR₁₅; provided that at least one of R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, and R₁₀ is (A), and provided that at least one of the remaining R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, and R₁₀ is COR₁₄ or NO₂; R₁₁ is for example C₁-C₂₀alkyl, M or (B); X and X₁ are for example a direct bond; R₁₂ and R′₁₂ are for example hydrogen or C₁-C₂₀alkyl; R₁₃ and R′₁₃ are for example C₆-C₂₀aryl or C₃-C₂₀heteroaryl; M is (X), (Y) or (Z); X₃ is O, S or NR₁₉; R₁₄ and R₁₅ are for example phenyl; R₂₀, R₂₁, R₂₂, R₂₃, R₂₄, or R₂₅ for example are hydrogen, COR₁₄, NO₂, or (B); provided that at least two oxime ester groups are present in the molecule; are useful as photoinitiators.

Claims

1. A compound of formula (I):

2. The compound of claim 1, wherein:

R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, and R₁₀ independently of each other are hydrogen, C₁-C₂₀alkyl,

3. The compound of claim 1, wherein:

R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ independently of each other are hydrogen,

4. A photopolymerizable composition, comprising

(a) at least one ethylenically unsaturated photopolymerizable compound;

and

(b) as photoinitiator, at least one compound of claim 1.

5. The photopolymerizable composition according to claim 4, wherein the component (a) is a resin obtained by reaction of a saturated or unsaturated polybasic acid anhydride with a product of the reaction of an epoxy resin and an unsaturated monocarboxylic acid.

6. The photopolymerizable composition according to claim 4, further comprising at least one of a further photoinitiator (c) and an additive (d).

7. The photopolymerizable composition according to claim 6, comprising, as the additive (d), a pigment or a mixture of pigments or a mixture of one or more pigments with one or more dyes.

8. The photopolymerizable composition according to claim 6, comprising, as the additive (d), a dispersant or a mixture of dispersants.

9. The photopolymerizable composition of claim 6, comprising, as the additive (d), a photosensitizer.

10. The photopolymerizable composition of claim 4, comprising 0.05 to 25% by weight of the photoinitiator (b), based on a total weight of the composition.

11. The photopolymerizable composition of claim 4, further comprising a binder polymer (e).

12. A process for photopolymerizing compounds containing ethylenically unsaturated double bonds, the process comprising irradiating the composition according to claim 4 with electromagnetic radiation in the range from 150 to 600 nm, or with electron beam or with X-rays, to form a polymer product.

13. The process of claim 12, wherein the polymer product is a component within at least one article selected from the group consisting of a pigmented paint, a nonpigmented paint, a pigmented varnish, a nonpigmented varnish, a powder coating, a printing ink, a printing plate, an adhesive, a pressure sensitive adhesive, a dental composition, a gel coat, a photoresist for electronics, an etch resist, a liquid film, a dry film, a solder resist, a resist to manufacture color filters, a resist to generate structures in the manufacturing processes of plasma-display panels, an electroluminescence display, an LCD, an article for encapsulating electrical and electronic components, an article for producing magnetic recording materials, a micromechanical part, a waveguide, an optical switch, a plating mask, a color proofing system, a glass fibre cable coating, a screen printing stencil, an article for producing three-dimensional objects by stereolithography, an image recording material for holographic recordings, a microelectronic circuit, a, decolorizing material, a formulation comprising microcapsules, a photoresist material for a UV and visible laser direct imaging system, and an article for forming dielectric layers in a sequential build-up layer of a printed circuit board.

14. A coated substrate which is coated on at least one surface with the composition according to claim 4.

15. A process for photographic production of relief images, the process comprising subjecting the coated substrate according to claim 14 to imagewise exposure and then removing unexposed portions with a developer.

16. A process for preparing the compound of claim 1, the process comprising reacting a corresponding oxime compound with an acyl halide of formula (II) or an anhydride of formula (III):

17. A color filter prepared by providing red, green and blue picture elements and a black matrix, all comprising a photosensitive resin and a pigment on a transparent substrate, and providing a transparent electrode either on the surface of the substrate or on the surface of the color filter layer, wherein said photosensitive resin comprises a polyfunctional acrylate monomer, an organic polymer binder and the compound of claim 1 as a photopolymerization initiator.

18. A process comprising photopolymerization of a composition comprising at least one ethylenically unsaturated photopolymerizable compound in the presence of the composition of claim 1.

19. A compound of formula (IA):