WO1998038195B1

WO1998038195B1 - PHOTOACTIVATABLE NITROGEN-CONTAINING BASES BASED ON α-AMMONIUM KETONES, IMINIUM KETONES OR AMIDINIUM KETONES AND ARYL BORATES

Info

Publication number: WO1998038195B1
Application number: PCT/EP1998/000846
Authority: WO
Filing date: 1998-02-14
Publication date: 1998-10-22

Abstract

This invention relates to α-ammonium ketones, iminium ketones or amidinium ketones in the form of their tetraaryl- or triarylalkylborate salts which can be photochemically converted into amines, imines or amidines as well as to a process for their preparation. This invention also relates to base-polymerisable or cross-linkable compositions comprising these α-ammonium ketones, iminium ketones or amidinium ketones in the form of their tetra- or triarylalkylborate salts, to a process for carrying out photochemically induced, base-catalysed reactions as well as to their use as photoinitiators for base-catalysed reactions.

Claims

54

AMENDED CLAIMS

[received by the International Bureau on 19 August 1998 (19.08.98); original claim 1 amended; remaining claims unchanged (4 pages)]

X is Cj-C.oalkylene, C -C₂oalkylene which is interrupted by -O-, -S- or NR₈, or X is

provided that, if R₁₂, Ri3, R_H and Rj₅ simultaneously are phenyl,

(a) R , R₃ and R₄ are not simultaneously methyl; and

(b) R₂, R₃ and R together are no

2. A compound according to claim 1 , wherein R- is phenyl, naphthyl, pyrenyl, thioxanthyl or penothiazinyl, which radicals are unsubstituted or mono- or polysubstituted by C C₁₈alkyl, C C₁₈haloalkyl, NR₆R₇ , CN, NO₂₎ SR₈ or OR₈.

3. A compound according to claim 1 , wherein R , R₃ and R₄ are each independently of one another hydrogen, C C₁₈alkyl, or R₂ and R₃, and/or R₄ and R₃ form each independently of one another a C₂-C₁₂alkylene bridge; or

R₂, R₃, R ₎ together with the linking nitrogen, are a group of the structural formulae (a), (b), (c), (d), (e), (f), (g), (h) or a phosphazene base of the P P₂ or P <t/4> type.

4. A compound according to claim 1 , wherein R₂, R₃ and R₄ are each independently of one another C C₁₈alkyl, or

R_2> R₃, R , together with the nitrogen atom, are a group of the structural formula (a), (b), (c),- (d) or (e).

AMENDED SHEET AfffiCL 55

5. A compound according to claim 1 , wherein R₁₂, R₁₃, Rι₄ are phenyl, biphenyl, naphthyl, anthracyl or penanthryl, which radicals are unsubstituted or mono- or polysubstituted by C C₁₈alkyl, C_rC₁₈haloalkyl, NO₂, OH, CN, OR₈, or halogen, and

R₁₅ is C_rC₁₈alkyl or phenyl which is unsubstituted or mono- or polysubstituted by C C₁₈alkyl, C C₁₈haloalkyl, NO₂, OH, CN, OR₈ or halogen.

6. A process for the preparation of a compound of formula I, which comprises reacting in a first step a nitrogenous base of formula II

NR₂R₃R₄ (II) with an α- halogen ketone of formula III

Halogen

CH R, (HI)

R O

to a compound of formula IV

R '₃3

R I + N — R,

-CH Halogen (IV)

R; ,R, m

and, in a second step, reacting the compound of formula IV with a compound of formula V

to the compound of formula I, wherein halogen is bromo or iodo, and M is Na, K or ammonium, and Rj, R₂, R₃, R₄, R₅, R₁₂, Rι_, R₁₄ and R₁₅ have the meanings and preferred meanings claimed in claim 1.

7. A composition, which comprises

A) at least one compound of formula (I), and B) at least one organic compound which is capable of a base-catalysed addition reaction or substitution reaction.

8. A composition according to claim 7, wherein component B) is an anionically polymerisable or crosslinkable organic material.

9. A composition according to claim 7, wherein component B) is one of the following systems: a) an acrylate copolymer having alkoxysilane or alkoxysiloxane side groups, b) a two-component system comprising a hydroxyl group-containing polyacrylate and/or polyester and an aliphatic or aromatic polyisocyanate, c) a two-component system comprising a functional polyacrylate and a polyepoxide, where the polyacrylate contains carboxyl or anhydride groups, d) a two-component system comprising a fluorine-modified or silicone-modified hydroxyl group-containing polyacrylate or polyester and an aliphatic or aromatic polyisocyanate, e) a two-component system comprising a (poly)ketimine and an aliphatic or aromatic polyisocyanate, f) a two-component system comprising a (poly)ketimine and an unsaturated acrylate resin or an acetoacetate resin or methyl α-acrylamidomethylglycolate, h) a two-component system comprising a (poly)oxazolidine and a polyacrylate containing anhydride groups, or an unsaturated acrylate resin or a polyisocyanate, i) a two-component system comprising an epoxy group-containing polyacrylate and a carboxyl group-containing polyacrylate,

I) a polymer based on allyl glycidyl ether, m) a two-component system comprising a (poly)alcohol and a (poly)isocyanate, n) a two-component system comprising an α,β-ethylenically unsaturated carbonyl compound and a compound which contains activated CH₂ groups.

10. A composition according to claim 7, wherein component B) is one of the following systems: b) a two-component system comprising a hydroxyl group-containing polyacrylate and/or polyester and an aliphatic or aromatic polyisocyanate, c) a two-component system comprising a functional polyacrylate and a polyepoxide, where" the polyacrylate contains carboxyl or anhydride groups, 57

i) a two-component system comprising an epoxy group-containing polyacrylate and a carboxyl group-containing polyacrylate, m) a two-component system comprising a (poly)alcohol and a (poly)isocyanate, and n) a two-component system comprising an ,β-ethylenically unsaturated carbonyl compound and a compound which contains activated CH₂ groups.

11. A composition according to claim 7, wherein component B is an epoxy resin or a mixture of different epoxy resins.

12. A composition according to claim 7, wherein component A) is present in an amount of 0.01 to 10 % by weight, based on component B).

13. A composition according to claim 7, which additionally comprises a sensitiser selected from the group consisting of thioxanthones, oxazines, acridines, phenazines and rhodamines.

14. A process for carrying out base-catalysed reactions, which comprises exposing a composition according to claim 7 with light having a wavelength in the range from 200 nm to

650 nm.

15. A process according to claim 14, which comprises heating the composition before or after the exposure to light.

16. Use of an organic compound according to claim 1 as photoinitiator for photochemically induced base-catalysed addition reactions or substitution reactions.

17. Use of an organic compound according to claim 1 for the preparation of coatings, moulding compositions or photostructured layers.

18. A coated substrate, which is coated on at least one surface with a composition as claimed in claim 7.

19. A polymerised or crosslinked composition according to claim 7.