Oxime ester photoiniators having a combined structure

• US 20040170924A1
• Filed: 12/08/2003
• Published: 09/02/2004
• Est. Priority Date: 06/11/2001
• Status: Active Grant

• Current Assignee: BASF SE
• Original Assignee: CIBA Specialty Chemicals
• Inventors: Ohwa, Masaki, Tanabe, Junichi, Kunimoto, Kazuhiko, Oka, Hidetaka, Kura, Hisatoshi
• Granted Patent: US 7,189,489 B2
• Time in Patent Office: Days
• US Class Current: 430/281.1
• 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

each of which is unsubstituted or substituted 1 to 4 times by halogen, C₁-C₆alkyl, OR₃, SR₄ and/or NR₅R₆;

or each of which is substituted by a group, —

(CO)R₇, (D), (E) or (F);

or Ar₂ is

each of which is unsubstituted or substituted by 1 to 6 times by halogen, C₁-C₆alkyl, OR₃, SR₄ and/or NR₅R₆, wherein the substituents OR₃, SR₄ or NR₅R₆ optionally form 5- or 6-membered rings via the radicals R₃, R₄, R₅ and/or R₆ with one of the carbon atoms of the phenyl ring;

or each of which is substituted by a group —

(CO)R₇, (D), (E) or (F);

Ar₃ is phenyl, naphthyl or coumarinyl, each of which is substituted 1 to 7 times by halogen, C₁-C₁₂alkyl, phenyl or by phenyl which is substituted by one or more OR₃, SR₄ and/or NR₅R₆;

or each of which is substituted by OR₃, SR₄ and/or NR₅R₆;

M₁ is C₁-C₂₀alkylene, which is optionally interrupted by one or more —

O—

;

or M₁ is phenylene or naphthylene, each of which is unsubstituted or substituted by one or more C₁-C₆alkyl, phenyl, halogen, OR₃, SR₄ and/or NR₅R₆;

or M₁ is a group (H), which is optionally substituted 1 to 4 times by halogen, C₁-C₆alkyl, OR₃, SR₄ and/or NR₅R₆, wherein the substituents OR₃, SR₄ or NR₅R₆ optionally form 5- or 6-membered rings via the radicals R₃, R₄, R₅ and/or R₆ with one of the carbon atoms of the other phenyl ring;

M₂ is a direct bond, C₁-C₁₀alkylene or C₁-C₁₀alkylene-O—

, each of which is optionally interrupted by one or more —

O—

;

or M₂ is phenylene-O—

, which is unsubstituted or substituted by one or more C₁-C₆alkyl, phenyl, halogen, OR₃, SR₄ and/or NR₅R₆;

or M₂ is C₁-C₆alkylenephenylene-O—

;

M₃ and M₃′

independently each other are a direct bond, or are C₁-C₁₀alkylene or C₁-C₁₀alkylene-X—

, each of which is optionally interrupted by one or more —

O—

;

or M₃ and M₃′

are phenylene or phenylene-X—

, each of which is unsubstituted or substituted by one or more C₁-C₆alkyl, phenyl, halogen, OR₃, SR₄ and/or NR₅R₆;

or M₃ and M₃′

are C₁-C₁₀alkylene-C(O)—

X—

, C₁-C₁₀alkylene-X—

C(O)—

, phenylene-C(O)—

X—

, C₁-C₆alkylene-phenylene-X—

or phenylene-(CO)-phenylene;

M₄ and M₄′

independently of each other are a direct bond, —

O—

, —

S—

, —

NR₅′

—

or —

CO—

;

or M₄ and M₄′

are —

Y—

(C₁-C₁₀alkylene)-Y′

—

which is optionally interrupted by one or more —

O—

;

or M₄ and M₄′

are —

Y-phenylene-Y′

—

, each of which is unsubstituted or substituted by one or more C₁-C₆alkyl, phenyl, halogen, OR₃, SR₄ and/or NR₅R₆;

or M₄ and M₄′

are —

Y—

(C₁-C₄alkylene)-O-phenylene-O—

(C₁-C₄alkylene)-Y′

—

or —

Y—

(C₁-C₄alkylene)-O-naphthylene-O-(C₁-C₄alkylene)-Y′

—

, or M₄ and M₄′

are —

X-C₁-C₁₀alkylene-X—

C(O)—

which is optionally interrupted by one or more —

O—

;

or M₄ and M₄′

are a group

which is optionally substituted 1 to 4 times by halogen, C₁-C₁₂alkyl, OR₃, SR₄ and/or NR₅R₆, wherein the substituents OR₃, SR₄ or NR₅R₆ optionally form 5- or 6-membered rings via the radicals R₃, R₄, R₅ and/or R₆ with one of the carbon atoms of the other phenyl ring or that of the phenyl ring attached to this group;

M₄″

is a direct bond, —

O—

, —

S—

, —

NR₅′

—

or —

CO—

;

or M₄″

is —

Y—

(C₁-C₁₀alkylene)-Y′

—

which is optionally interrupted by one or more —

O—

;

or M₄″

is —

Y-phenylene-Y′

—

, which is unsubstituted or substituted by one or more C₁-C₆alkyl, phenyl, halogen, OR₃, SR₄ and/or NR₅R₆;

or M₄″

is —

X—

C₁-C₁₀alkylene-X—

C(O)—

which is optionally interrupted by one or more —

O—

;

R₃ is hydrogen, C₁-C₂₀alkyl or phenyl-C₁-C₃alkyl;

or R₃ is C₁-C₈alkyl which is substituted by C₃-C₆alkenoxy, —

O(CO)—

(C₁-C₄alkyl) or —

O(CO)-phenyl;

or R₃ is C₂-C₁₂alkyl which is interrupted by one or more —

O—

;

or R₃ is C₁-C₈alkanoyl;

or benzoyl which is unsubstituted or substituted by one or more C₁-C₆alkyl, halogen and/or C₁-C₄alkoxy;

or R₃ is phenyl or naphthyl each of which is unsubstituted or substituted by halogen, C₁-C₁₂alkyl, C₁-C₄alkoxy, C₁C₁₂alkylsulfanyl, phenylsulfanyl, —

N(C₁-C₁₂alkyl)₂ and/or diphenylamino;

R₄ is hydrogen, C₁-C₂₀alkyl or phenyl-C₁-C₃alkyl;

or R₄ is C₁-C₈alkyl which is substituted by C₃-C₆alkenoxy, —

O(CO)—

(C₁-C₄alkyl) or —

O(CO)-phenyl;

or R₄ is C₂-C₁₂alkyl which is interrupted by one or more —

O—

or —

S—

;

or R₄ is C₁-C₈alkanoyl;

or benzoyl which is unsubstituted or substituted by one or more C₁-C₆alkyl, halogen, C₁-C₄alkoxy or C₁-C₄alkylsulfanyl;

or R₄ is phenyl or naphthyl, each of which is unsubstituted or substituted by halogen, C₁-C₁₂alkyl, C₁-C₁₂alkoxy, phenoxy, C₁-C₁₂alkylsulfanyl, phenylsulfanyl, —

N(C₁-C₁₂alkyl)₂, diphenylamino or —

(CO)(C₁-C₈alkyl);

R₅ and R₆ independently of each other are hydrogen, C₁-C₂₀alkyl, C₂-C₁₀alkoxyalkyl, phenyl-C₁-C₃alkyl, C₁-C₈alkanoyl or benzoyl;

or R₅ and R₆ are phenyl or naphthyl, each of which is unsubstituted or substituted by benzoyl, C₁-C₁₂alkyl or C₁-C₁₂alkoxy;

or R₅ and R₆ together are C₂-C₆alkylene optionally interrupted by —

O—

or —

NR₃— and

/or optionally substituted by C₁-C₄alkoxy, C₂-C₄alkanoyloxy or benzoyloxy;

R₅′

is hydrogen, C₁-C₁₀alkyl or C₂-C₄hydroxyalkyl;

or R₅′

is phenyl or naphthyl, each of which is unsubstituted or substituted by C₁-C₆alkyl or C₁-C₆alkoxy;

or R₅′

is a group

R₇ is hydrogen, C₁-C₂₀alkyl;

C₁-C₈alkyl which is substituted by phenyl, —

OH, —

O(CO)—

(C₁-C₄alkyl) or —

O(CO)-phenyl;

or R₇ is C₂-C₅alkenyl or C₃-C₈cycloalkyl;

or R₇ is phenyl, biphenylyl or naphthyl, each of which optionally is substituted by one or more C₁-C₆alkyl, halogen, CN, OR₃, SR₄ or NR₅R₆;

R₈, R₉, R₈′ and

R₉′

independently of each other are hydrogen, C₁-C₆alkyl;

phenyl optionally substituted by one or more C₁-C₆alkyl, halogen, OR₃, SR₄ or NR₅R₆;

or R₈, R₉, R₈′ and

R₉′

are halogen, OR₃, SR₄ or NR₅R₆, wherein the substituents OR₃, SR₄ or NR₅R₆ optionally form 5- or 6-membered rings via the radicals R₃, R₄, R₅ and/or R₆ with one of the carbon atoms of the phenyl, naphthyl or benzopyl group of Ar₁ or that of the substituent R₇;

or R₈ and R₉ or R₈′ and

R₉′

together are a group

and

R₁₀, R₁₁, R₁₂ and R₁₃ independently of one another are hydrogen, C₁-C₆alkyl, phenyl, halogen, OR₃, SR₄ or NR₅R₆.

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

Ar₃ is naphthyl;

M₄ and M₄′

independently of each other are a direct bond, —

O—

, —

S—

, —

Y—

(C₁-C₁₀alkylene)-Y′

—

or —

Y—

(C₁-C₄alkylene)-O-phenylene-O—

(C₁-C₄alkylene)-Y′

—

;

Y and Y′

independently each other are a direct bond or —

O—

;

R₃ is C₁-C₁₂alkyl;

R₄ is phenyl, unsubstituted or substituted by —

(CO)(C₁-C₈alkyl);

R₅ and R₆ independently of each other are C₁-C₁₂alkyl;

or are phenyl, which unsubstituted or substituted by benzoyl or C₁-C₁₂alkyl;

R₇ is phenyl, biphenylyl or naphthyl, each of which optionally is substituted by one or more C₁-C₆alkyl, halogen, OR₃, SR₄ or NR₅R₆; and

R₈ and R₉ are hydrogen or NR₅R₆, wherein the substituents NR₅R₆ optionally form 5- or 6-membered rings via the radicals R₅ or R₆ with on eof the carbon atoms of the phenyl, naphthyl or benzoyl group of Ar₁.

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 anyone of claims 4-5, 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 5 or 6 as further additive (d) comprising a photosensitizer, in particular a compound 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 to anyone of claims 4-7 additionally comprising a binder polymer (e), in particular a copolymer of methacrylate and methacrylic acid.

9. A process for the photopolymerization of compounds containing ethylenically unsaturated double bonds, which comprises irradiating a composition according to anyone of claims 4-8 with electromagnetic radiation in the range from 150 to 600 nm, or with electron beam or with X-rays.

10. The use of a composition according to anyone of the claims 4-8 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, 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 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, for producing three-dimensional objects by means of stereolithography, and as image recording material, especially for holographic recordings, microelectronic circuits, decolorizing materials, decolorizing materials for image recording materials, for image recording materials using microcapsules, is 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.

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 like electroplating resist, etch resist, both liquid and dry films, solder resist, 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, composite compositions, resists, including photoresists, 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, especially for holographic recordings, microelectronic circuits, decolorizing materials for image recording materials using microcapsules, for forming dielectric layers in a sequential build-up layer of a printed circuit board, especially a process using UV and visible laser as a light source of a direct imaging technique.

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.