Oxime ester photoiniators having a combined structure

• US 7,189,489 B2
• Filed: 06/04/2002
• Issued: 03/13/2007
• Est. Priority Date: 06/11/2001
• Status: Expired due to Term

• Current Assignee: BASF SE
• Original Assignee: CIBA Specialty Chemicals
• Inventors: Ohwa, Masaki, Tanabe, Junichi, Oka, Hidetaka, Kura, Hisatoshi, Kunimoto, Kazuhiko
• Primary Examiner(s): WALKE, AMANDA C
• Application Number:
  US10/480,146
• Publication Number:
  US 20040170924A1
• Time in Patent Office: 1,743 Days
• Field of Search: 430/270.1, 562/30, 562/58
• US Class Current: 430/270.1
• CPC Class Codes: C07C 251/66 with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
• CPC Class Codes: C08F 2/50 with sensitising agents
• CPC Class Codes: G03F 7/031 Organic compounds not covered by group G03F7/029

Abstract

Compounds of the formulae I, II and III

wherein R₁ is for example hydrogen, C₃–C₈cycloalkyl, C₁–C₁₂alkyl, phenyl unsubstituted or substituted; R₂ and R₂′ for example are hydrogen, C₁–C₂₀alkyl, C₃–C₈cycloalkyl or phenyl, unsubstituted or substituted, or are

Ar₁ is for example phenyl, optionally substituted by e.g.

Ar₂ is for example phenylene, optionally substituted e.g. by —(CO)R₇, (D), (E) or (F); Ar₃ is for example phenyl; M₁, M₂ and M₃ are, for example, C₁–C₂₀alkylene; M₄ is for example direct bond, —O—, —S—, —Y—(C₁–C₁₀alkylene)-Y′—, optionally substituted; Y and Y′ are for example a direct bond or —O—; R₇ is for example hydrogen, C₁–C₂₀alkyl or phenyl, optionally substituted; R₈, R₉, R₈′ and R₉′ are for example hydrogen or C₁–C₁₂alkyl, exhibit an unexpectedly good performance in photopolymerization reactions.

Claims

1. Compounds of the formulae I, II and III

2. Compounds of the formulae I, II and III according to claim 1, wherein

R₁ is C₃–

C₆cycloalkyl or C₁–

C₆alkyl which is unsubstituted or substituted by one or more halogen or phenyl;

or R₁ is phenyl which is unsubstituted or substituted by one or more C₁–

C₆alkyl, halogen, OR₃, SR₄ and/or NR₅R₆;

or R₁ is C₁–

C₆alkoxy or benzyloxy;

R₂ and R₂′

independently of each other are hydrogen;

C₁–

C₂₀alkyl optionally substituted by one or more halogen, OR₃, phenyl and/or phenyl substituted by OR₃, SR₄ and/or NR₅R₆;

or are C₃–

C₆cycloalkyl;

or are C₂–

C₂₀alkyl interrupted by one or more —

O— and

/or optionally substituted by one or more halogen, OR₃, phenyl and/or phenyl substituted by OR₃, SR₄ and/or NR₅R₆;

or R₂ and R₂′

are phenyl which is unsubstituted or substituted by one or more C₁–

C₆alkyl, phenyl, halogen, OR₃, SR₄ and/or NR₅R₆;

or R₂ and R₂′

are C₂–

C₁₂alkanoyl, C₂–

C₁₂alkoxycarbonyl or a group (A), (B) or (C);

Ar₁ is phenyl, naphthyl or benzoyl, each of which is substituted 1 to 7 times by halogen, C₁–

C₆alkyl, OR₃, SR₄ and/or NR₅R₆;

or each of which is substituted by phenyl or phenyl which is substituted by one or more OR₃, SR₄ or NR₅R₆;

or each of which is substituted by a group —

(CO)R₇, (D), (E) and/or (F);

Ar₂ is phenylene or phenylenedicarbonyl, each of which is substituted 1 to 4 times by halogen, C₁–

C₆alkyl, OR₃, SR₄ and/or NR₅R₆;

or Ar₂ is

3. Compounds of the formula I or III according to claim 1, wherein

R₁ is C₁–

C₁₂alkyl or phenyl;

R₂ and R₂′

are hydrogen, C₁–

C₁₂alkyl, phenyl or C₂–

C₁₂alkoxycarbonyl;

Ar₁ is phenyl, naphthyl or benzoyl, each of which is substituted by OR₃ or NR₅R₆, wherein the substituents, NR₅R₆ optionally form 5- or 6-membered rings via the radicals R₅ or R₆ with further substituents on the phenyl or naphthyl ring;

or each of which is substituted by a group —

(CO)R₇, (D), (E) or (F);

Ar₂ is

4. A photopolymerizable composition comprising

(a) at least one ethylenically unsaturated photopolymerizable compound and

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

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

6. A photopolymerizable composition according to claim 5, comprising 0.05 to 25% by weight of the photoinitiator (b), or the photoinitiators (b) and (c), based on the composition.

7. A photopolymerizable composition according to claim 6 comprising as further additive (d) a photosensitizer selected from the group consisting of benzophenone and its derivatives, thioxanthone and its derivatives, anthraquinone and its derivatives, or coumarin and its derivatives.

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

9. A process for the photopolymerization of compounds containing ethylenically unsaturated double bonds, which comprises irradiating a composition according to claim 4 with electromagnetic radiation in the range from 150 to 600 nm, or with electron beam or with X-rays.

10. A process for producing pigmented and nonpigmented paints and varnishes, powder coatings, printing inks, printing plates, adhesives, dental compositions, gel coats, photoresists for electronics, etch resists, both liquid and dry films, solder resists, as 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, as compositions 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, for producing three-dimensional objects by means of stereolithography, and as image recording material, 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, as a photoresist material used for forming dielectric layers in a sequential build-up layer of a printed circuit board, which comprises a step of polymerizing a photopolymerizable composition according to claim 4 with electromagnetic radiation in the range from 150 to 600 nm, or with electron beam or with X-rays.

11. A process according to claim 9 for producing pigmented and non-pigmented paints and varnishes, powder coatings, printing inks, printing plates, adhesives, dental compositions, gel coats, photoresists for electronics applications selected from the group consisting of electroplating resists, etch resists, both liquid and dry films, solder resists, as 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 LCDs, composite compositions, color filter materials, compositions 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, for producing three-dimensional objects by means of microlithography, plating, stereolithography, for producing image recording materials, microelectronic circuits, decolorizing materials for image recording materials using microcapsules, and for forming dielectric layers in a sequential build-up layer of a printed circuit board.

12. Coated substrate which is coated on at least one surface with a composition according to claim 4.

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

14. 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 a photopolymerization initiator of formula I, II or/and III according to claim 1.

15. A photo polmerizable composition according to claim 8, which additionally comprises as binder polymer (e) a copolymer of methacrylate and methacrylic acid.

16. A process for producing electroplating resists or holographic recordings, which comprises a step of polymerizing a photopolymerizable composition according to claim 4 with electromagnetic radiation in the range from 150 to 600 nm, or with electron beam or with X-rays.

17. A process according to claim 9, wherein UV and visible lasers are employed as the light source in a direct imaging technique.