Photoinitiator mixtures

Abstract

Photoinitiator mixture comprising at least one alpha-amino ketone compound; and at least one compound of the Formula (I) or (I) wherein R.sub.1 and R.sub.1 for example are hydrogen, C.sub.3-C.sub.8cycloalkyl or C.sub.1-C.sub.12alkyl R.sub.2 and R.sub.2 for example are hydrogen; unsubstituted C.sub.1-C.sub.20alkyl or substituted C.sub.1-C.sub.20alkyl; and R.sub.8 and R.sub.9 for example are hydrogen, C.sub.1-C.sub.12alkyl which optionally is substituted, or phenyl which optionally is substituted; exhibit an unexpectedly good performance in photopolymerization reactions. ##STR00001##

Claims

1. Photoinitiator mixture comprising: at least one alpha-amino ketone compound; and at least one the following compounds ##STR00090## ##STR00091##

2. A photopolymerizable composition comprising (a) at least one ethylenically unsaturated photopolymerizable compound and (b) a photoinitiator mixture as defined in claim 1.

3. A photopolymerizable composition according to claim 2, wherein the component (a) is a resin obtained by the reaction of a saturated or unsaturated polybasic acid anhydride with a product of the reaction of an epoxy resin and an unsaturated monocarboxylic acid.

4. A photopolymerizable composition according to claim 2, additionally to the photoinitiator (b) comprising at least one further photoinitiator (c), and/or other additives (d).

5. A photopolymerizable composition according to claim 4 as further additive (d) comprising a pigment or a mixture of pigments.

6. A photopolymerizable composition according to claim 4 as further additive (d) comprising a dispersant or a mixture of dispersants.

7. A photopolymerizable composition according to claim 4 as further additive (d) comprising 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 to claim 2, comprising 0.01 to 25% by weight of the photoinitiator (b), or the photoinitiators (b) and (c), based on the solid composition.

9. A photopolymerizable composition according to claim 2 additionally comprising a binder polymer (e), which is a copolymer of methacrylate and methacrylic acid.

10. A photopolymerizable composition according to claim 2, which is a printing ink.

11. A process for the photopolymerization of compounds containing ethylenically unsaturated double bonds, which comprises irradiating a composition according to claim 2 with electromagnetic radiation in the range from 150 to 600 nm, or with electron beam or with X-rays.

12. A composition according to claim 2 for producing pigmented and nonpigmented paints and varnishes, powder coatings, printing inks, printing plates, adhesives, pressure sensitive adhesives, dental compositions, gel coats, photoresists for electronics, electroplating resists, etch resists, both liquid and dry films, solder resists, resists to manufacture color filters for a variety of display applications, resists 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, for producing three-dimensional objects by means of stereolithography, 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, as a photoresist material used for forming dielectric layers in a sequential build-up layer of a printed circuit board.

13. 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 photoinitiator mixture as defined in claim 1.

14. Coated substrate which is coated on at least one surface with a composition according to claim 2.

15. A photopolymerizable composition according to claim 3, comprising at least one further photoinitiator (c), and/or other additives (d).

16. A photopolymerizable composition according to claim 15 comprising 0.01 to 25% by weight of the photoinitiator (b), or the photoinitiators (b) and (c), based on the solid composition, as further additive (d) comprising a pigment or a mixture of pigments, a dispersant or a mixture of dispersants, or 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.

17. A photopolymerizable composition according to claim 16, additionally comprising a binder polymer (e), which is a copolymer of methacrylate and methacrylic acid.

18. A photoinitiator mixture according to claim 1, wherein the alpha-amino ketone compound is of the formula (AK) ##STR00092## wherein R.sub.25 and R.sub.26 independently of one another are hydrogen, C.sub.1-C.sub.20alkyl, phenyl, SR.sub.33, OR.sub.34 or NR.sub.35R.sub.36; R.sub.27 and R.sub.28 independently of one another are hydrogen, C.sub.1-C.sub.20alkyl, C.sub.1-C.sub.20hydroxyalkyl or C.sub.2-C.sub.20alkyl which is interrupted by one or more O; or R.sub.27 and R.sub.28 together with the N-atom to which they are attached form a 5- or 6-membered saturated ring, which optionally as further heteroatom comprises O, S or NR.sub.31; provided that at least one of R.sub.27 and R.sub.28 is other than hydrogen R.sub.29 and R.sub.30 independently of one another are C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkenyl or ##STR00093## or R.sub.29 and R.sub.30 together with the carbon atom to which they are attached form a 5- or 6-membered saturated ring; R.sub.31 and R.sub.32 independently of one another are hydrogen, C.sub.1-C.sub.20alkyl, phenyl or C.sub.2-C.sub.20alkenyl; R.sub.33 and R.sub.34 independently of one another are hydrogen, C.sub.1-C.sub.20alkyl, C.sub.1-C.sub.20hydroxyalkyl, CH.sub.2CH.sub.2O[(CO)C.sub.5H.sub.10O].sub.zH, phenyl, cylopentyl, cyclohexyl or C.sub.2-C.sub.20alkenyl; R.sub.35 and R.sub.36 independently of one another are hydrogen, C.sub.1-C.sub.20alkyl, C.sub.1-C.sub.20hydroxyalkyl or C.sub.2-C.sub.20alkyl which is interrupted by one or more O, or R.sub.35 and R.sub.36 together with the N-atom to which they are attached form a 5- or 6-membered saturated or unsaturated, aliphatic or aromatic ring, which optionally as further heteroatom comprises O, S or NR.sub.37; R.sub.37 has one of the meanings as given for R.sub.35 or is ##STR00094## R.sub.38 is hydrogen, ##STR00095## Y.sub.1 and Y.sub.2 independently of one another are C.sub.1-C.sub.20alkylene; and z is an integer of 1-10.

Description

EXAMPLE 1

(1) Synthesis of

(2) ##STR00062##

Compound of Formula I; R1R2CH3, R7=Phenyl Substituted by CH3

1.a. 1-(4-{(4-Acetyl-phenyl)-[4-(3-methyl-benzoyl)-phenyl]-amino}-phenyl)-ethanone

(3) To triphenylamine (5.00 g) in CH.sub.2Cl.sub.2 (80 mL) are added AlCl.sub.3 (2.89 g) and m-toluoyl chloride (3.15 g) at 0 C. After stirring overnight at room temperature, AlCl.sub.3 (5.98 g) and acetyl chloride (3.36 g) are further added at 0 C. After the mixture is stirred at room temperature overnight, the reaction mixture is poured into ice-water, and the crude product is extracted twice with CH.sub.2Cl.sub.2. The combined organic layer is washed with H.sub.2O and brine, dried over MgSO.sub.4, and concentrated to give the product. The structure of the product, which is obtained as a yellow solid, is confirmed by the .sup.1H-NMR spectrum (CDCl.sub.3). [ppm]: 2.44 (s, 3H), 2.59 (s, 6H), 7.16-7.25 (m, 6H), 7.34-7.42 (m, 2H), 7.58 (d, 1H), 7.63 (s, 1H), 7.79 (d, 2H), 7.92 (d, 4H).

1.b

1-{4-([4-{1-(Acetoxyimino)-ethyl}-phenyl]-[4-(3-methyl-benzoyl)-phenyl]-amino)-phenyl}-ethan one oxime O-acetate

(4) The ketone 1.a is transformed to the corresponding oxime acetate 1.b, which is isolated as a yellow solid, according to the procedure described in WO02-100903. The structure is confirmed by the .sup.1H-NMR spectrum (CDCl.sub.3). [ppm]: 2.27 (s, 6H), 2.38 (s, 6H), 2.43 (s, 3H), 7.11 (d, 2H), 7.16 (d, 4H), 7.34-7.40 (m, 2H), 7.56 (d, 2H), 7.61 (s, 1H), 7.70 (d, 4H), 7.75 (d, 2H).

EXAMPLES 2-25

(5) The compounds of examples 2-15 are prepared according to the method as given in example 1 or in U.S. Pat. No. 6,596,445 or in WO 2007/062963 employing the appropriate educts. The compounds and their physical data are listed in table 1 below.

(6) TABLE-US-00001 TABLE 1 example Compound physical data 2 Yellow solid .sup.1H-NMR (CDCl.sub.3) [ppm]: 2.27 (s, 6H), 2.38 (s, 6H), 7.06 (d, 2H), 7.15 (d, 4H), 7.48-7.54 (m, 3H), 7.58 (d, 1H), 7.69 (d, 4H), 7.77 (d, 2H), 7.91 (m, 1H), 7.98 (d, 1H), 8.07 (m, 1H). formula I, R.sub.1 = R.sub.2 = CH.sub.3; R.sub.7 = naphthyl 3 Yellow solid .sup.1H-NMR (CDCl.sub.3) [ppm]: 2.27 (s, 6H), 2.38 (s, 6H), 7.08-7.18 (m, 7H), 7.24-7.28 (m, 2H), 7.38- 7.42 (m, 2H), 7.50-7.54 (m, 2H), 7.68-7.74 (m, 8H). formula I, R.sub.1 = R.sub.2 = CH.sub.3; R.sub.7 = phenyl substituted by SR.sub.4; R.sub.4 = phenyl 4 Yellow solid .sup.1H-NMR (CDCl.sub.3) [ppm]: 2.27 (s, 6H), 2.37 (s, 3H), 2.39 (s, 6H), 3.87 (s, 6H), 7.06 (s, 2H), 7.12 (d, 2H), 7.16 (d, 4H), 7.71 (d, 4H), 7.79 (d, 2H). formula I, R.sub.1 = R.sub.2 = CH.sub.3; R.sub.7 = phenyl substituted by OR.sub.3; R.sub.3 = C.sub.1 alkanoyl and CH.sub.3 5 Yellow solid .sup.1H-NMR (CDCl.sub.3) [ppm]: 2.27 (s, 6H), 2.39 (s, 6H), 7.11 (d, 2H), 7.16 (d, 4H), 7.61-7.74 (m, 10H). formula I, R.sub.1 = R.sub.2 = CH.sub.3; R.sub.7 = phenyl substituted by halogen 6 Yellow solid .sup.1H-NMR (CDCl.sub.3) [ppm]: 2.27 (s, 6H), 2.38 (s, 6H), 7.05 (d, 2H), 7.15 (d, 4H), 7.34 (d, 2H), 7.38- 7.43 (m, 1H), 7.64 (d, 1H), 7.66- 7.71 (m, 6H). formula I, R.sub.1 = R.sub.2 = CH.sub.3; R.sub.7 = phenyl substituted by halogen 7 Yellow solid .sup.1H-NMR (CDCl.sub.3) [ppm]: 2.27 (s, 6H), 2.38 (s, 6H), 2.44 (s, 3H), 7.11 (d, 2H), 7.15 (d, 4H), 7.29 (d, 2H), 7.68-7.76 (m, 8H). formula I, R.sub.1 = R.sub.2 = CH.sub.3; R.sub.7 = phenyl substituted by CH.sub.3 8 Yellow solid .sup.1H-NMR (CDCl.sub.3) [ppm]: 2.27 (s, 6H), 2.35 (s, 3H), 2.38 (s, 6H), 7.06 (d, 2H), 7.15 (d, 4H), 7.22- 7.40 (m, 4H), 7.66-7.72 (m, 6H). formula I, R.sub.1 = R.sub.2 = CH.sub.3; R.sub.7 = phenyl substituted by CH.sub.3 9 0 Yellow solid .sup.1H-NMR (CDCl.sub.3) [ppm]: 2.27 (s, 6H), 2.39 (s, 6H), 7.12-7.18 (m, 7H), 7.68-7.72 (m, 6H), 7.83 (d, 2H). formula I, R.sub.1 = R.sub.2 = CH.sub.3; R.sub.7 = thienyl 10 Yellow solid .sup.1H-NMR (CDCl.sub.3) [ppm]: 2.27 (s, 6H), 2.39 (s, 6H), 7.16-7.22 (m, 6H), 7.32 (t, 2H), 7.44 (t, 2H), 7.53 (d, 2H), 7.70-7.76 (m, 6H), 7.85 (d, 2H), 8.06 (d, 2H), 8.15 (d, 2H). formula I, R.sub.1 = R.sub.2 = CH.sub.3; R.sub.7 = phenyl substituted by NR.sub.5R.sub.6; R.sub.5 and R.sub.6 form a heterocyclic ring 11 Yellow solid .sup.1H-NMR (CDCl.sub.3) [ppm]: 0.98 (d, 12H), 1.98 (quint, 2H), 2.26 (s, 6H), 2.44 (s, 3H), 2.77 (d, 4H), 7.10-7.20 (m, 6H), 7.26-7.31 (m, 2H), 7.64-7.77 (m, 8H). formula I, R.sub.1 = CH.sub.3; R2 = C.sub.4H.sub.9; R.sub.7 = phenyl substituted by CH.sub.3 12 Yellow oil .sup.1H-NMR (CDCl.sub.3) [ppm]: 0.89 (t, 6H), 1.20-1.44 (m, 16H), 1.54- 1.64 (m, 4H), 2.26 (s, 6H), 2.43 (s, 3H), 2.82 (t, 4H), 7.08-7.19 (m, 6H), 7.35-7.41 (m, 2H), 7.54- 7.59 (m, 1H), 7.60-7.63 (m, 1H), 7.67 (d, 4H), 7.75 (d, 2H). formula I, R.sub.1 = CH.sub.3; R.sub.2 = C.sub.7H.sub.15; R.sub.7 = phenyl substituted by CH.sub.3 13 Yellow solid .sup.1H NMR (CDCl.sub.3) [ppm]: 2.27 (s, 6H), 2.38 (s, 6H), 7.06 (d, 2H), 7.15 (d, 4H), 7.30-7.38 (m, 2H), 7.48 (d, 1H), 7.64-7.73 (m, 6H). formula I, R.sub.1 = R.sub.2 = CH.sub.3, R.sub.7 = phenyl substituted by two halogens 14 Yellow solid .sup.1H NMR (CDCl.sub.3) [ppm]: 2.27 (s, 6H), 2.38 (S, 6H), 7.11 (d, 2H), 7.16 (d, 4H), 7.49 (t, 2H), 7.58 (t, 1H), 7.70 (d, 4H), 7.75 (d, 2H), 7.79 (d, 2H). formula I, R.sub.1 = R.sub.2 = CH.sub.3; R.sub.7 = phenyl 15 Yellow solid .sup.1H NMR (CDCl.sub.3) [ppm]: 1.26 (t, 6H), 2.27 (s, 6H), 2.60 (t, 4H), 3.16 (t, 4H), 4.15 (q, 4H), 7.10- 7.20 (m, 6H), 7.49 (t, 2H), 7.56- 7.62 (m, 1H), 7.68 (d, 4H), 7.74- 7.82 (m, 4H). formula I, R.sub.1 = CH.sub.3; R.sub.2 = alkyl substituted by COOR.sub.3; R.sub.3 = ethyl; R.sub.7 = phenyl 16 Yellow solid .sup.1H-NMR (CDCl.sub.3) [ppm]: 2.44 (s, 3H), 2.53 (s, 6H), 7.15 (d, 2H), 7.21 (d, 4H), 7.36-7.42 (m, 2H), 7.51 (t, 4H), 7.56-7.66 (m, 4H), 7.78 (m, 6H), 8.14 (d, 4H). formula I, R.sub.1 = phenyl; R.sub.2 = CH.sub.3; R.sub.7 =phenyl substituted by CH.sub.3 17 Yellow solid .sup.1H-NMR (CDCl.sub.3) [ppm]: 1.39 (t, 6H), 2.39 (s, 6H), 2.43 (s, 3H), 4.36 (q, 4H), 7.11 (d, 2H), 7.16 (d, 4H), 7.34-7.41 (m, 2H), 7.40- 7.62 (m, 2H), 7.69 (d, 4H), 7.75 (d, 2H). formula I, R.sub.1 = ethoxy; R.sub.2 = CH.sub.3; R.sub.7 = phenyl substituted by CH.sub.3 18 Yellow solid .sup.1H NMR (CDCl.sub.3) [ppm]: 2.27 (s, 6H), 2.39 (s, 6H), 7.12 (d, 2H), 7.16 (d, 4H), 7.37 (d, 2H), 7.57 (d, 2H), 7.71 (d, 4H), 7.75 (d, 2H), 7.82 (d, 2H), 8.14 (d, 2H). formula I, R.sub.1 = R.sub.2 = CH.sub.3; R.sub.7 = phenyl substituted by SR.sub.4; R.sub.4 = phenyl substituted by NO.sub.2 19 0 Yellow solid .sup.1H NMR (CDCl.sub.3) [ppm]: 2.27 (s, 6H), 2.28 (s, 3H), 2.38 (s, 6H), 2.39 (s, 3H), 7.11 (d, 2H), 7.15 (d, 4H), 7.34 (d, 2H), 7.47 (d, 2H), 7.68-7.76 (m, 10H). formula I, R.sub.1 = R.sub.2 = CH.sub.3; R.sub.7 = phenyl substituted by SR.sub.4; R.sub.4 = phenyl substituted by 20 Yellow solid .sup.1H-NMR (CDCl.sub.3) [ppm]: 2.28 (s, 6H), 2.31 (s, 6H), 2.40 (s, 6H), 2.55 (s, 6H), 7.16-7.22 (m, 6H), 7.50 (d, 2H), 7.68-7.76 (m, 6H), 7.86 (d, 2H), 7.93 (d, 2H), 8.09 (d, 2H), 8.60 (s, 2H). formula I, R.sub.1 = R.sub.2 = CH.sub.3; R.sub.7 = phenyl substituted by NR.sub.5R.sub.6; R.sub.5 and R.sub.6 form a heterocyclic ring substituted by two 21 Yellow solid .sup.1H NMR (CDCl.sub.3) [ppm]: 0.90 (t, 3H), 1.32-1.38 (m, 4H), 1.62- 1.70 (m, 2H), 2.27 (s, 6H), 2.39 (s, 6H), 2.69 (t, 2H), 7.12 (d, 2H), 7.16 (d, 4H), 7.29 (d, 2H), 7.70 (d, 4H), 7.72-7.76 (m, 4H). formula I, R.sub.1 = R.sub.2 = CH.sub.3; R.sub.7 = phenyl substituted by n-pentyl. 22 Yellow solid .sup.1H NMR (CDCl.sub.3) [ppm]: 1.09 (d, 6H), 1.19 (d, 6H), 1.27 (d, 6H), 2.27 (s, 6H), 2.38 (s, 6H), 2.68 (quint, 2H), 2.92 (quint, 1H), 7.04 (s, 2H), 7.04 (d, 2H), 7.14 (d, 4H), 7.67 (d, 6H). formula I, R.sub.1 = R.sub.2 = CH.sub.3; R.sub.7 = phenyl substituted by three isopropyl groups. 23 Yellow solid .sub.1H NMR (CDCl.sub.3) [ppm]: 2.17 (quint, 4H), 2.24 (s, 6H), 2.44 (s, 3H), 3.05 (t, 4H), 3.44 (t, 4H), 7.06 (d, 2H), 7.11 (d, 4H), 7.28 (dd, 2H), 7.37-7.42 (m, 4H), 7.58 (d, 1H), 7.61 (s, 1H), 7.68 (d, 4H), 7.72 (d, 2H), 7.74 (d, 2H), 7.82 (d, 2H). formula I, R.sub.1 = CH.sub.3; R.sub.2 = propyl substituted by SR.sub.4; R.sub.4 = heteroaryl; R.sub.7 = phenyl substiuted by CH.sub.3 24 Yellow solid .sup.1H NMR (CDCl.sub.3) [ppm]: 0.89 (t , 6H), 1.24-1.44 (m, 12H), 1.63 (quint, 4H), 2.18 (s, 6H), 2.20 (s, 6H), 2.35 (s, 3H), 2.86 (t, 4H), 7.14 (d, 2H), 7.19 (d, 4H), 7.22- 7.34 (m, 4H), 7.37 (d, 4H), 7.73 (d, 2H). formula I, R.sub.1 = CH.sub.3; R.sub.2 = phenyl substituted by CH.sub.3; R.sub.22 = n-C.sub.6H.sub.13; R.sub.23 = CH.sub.3; m = 1; X.sub.2 = direct bond. 25 Yellow liquid .sup.1H NMR (CDCl.sub.3) [ppm]: 0.87 (t, 6H), 1.24-1.42 (m, 12H), 1.55 (quint, 4H), 2.26 (s, 6H), 2.37 (s, 3H), 2.79 (t, 4H), 7.18 (d, 6H), 7.24-7.42 (m, 4H), 7.77 (d, 2H), 8.06 (d, 4H). formula I, R.sub.1 = CH.sub.3; R.sub.2 = n-C.sub.6H.sub.13; R7 = phenyl substituted by CH.sub.3.

EXAMPLE 16

Synthesis of 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone

(7) The compound is prepared according to the method as given in U.S. Pat. No. 5,077,402 (compound No. 10 in Table I).

APPLICATION EXAMPLES

(8) In the following examples the following photoinitiator mixtures are employed: PM-1 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone and compound (8) in the ratio 96/4 PM-2 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone and compound (8) in the ratio 92.5/7.5 PM-3 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone and compound (8) in the ratio 90/10 PM-4 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone and compound (8) in the ratio 98/2 PM-5 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone and compound (8) in the ratio 94/6 PM-6 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone and compound (8) in the ratio 92/8 PM-7 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone and compound (9) in the ratio 96/4 PM-8 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone and compound (9) in the ratio 94/6 PM-9 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone and compound (9) in the ratio 92/8 PM-10 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone and compound (9) in the ratio 90/10 PM-11 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone and compound (21) in the ratio 98/2 PM-12 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone and compound (21) in the ratio 96/4 PM-13 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone and compound (21) in the ratio 94/6 PM-14 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone and compound (21) in the ratio 92/8 PM-15 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone and compound (21) in the ratio 90/10 PM-16 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone and compound (9) in the ratio 92/8 PM-17 2-(4-methylbenzyl)-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone and compound (8) in the ratio 92/8 PM-18 2-benzyl-2-(dimethylamino)-1-(3,4-dimethoxyphenyl)-1-butanone and compound (8) in the ratio 92/8 PM-19 2-methyl-1-[4-methylthio]phenyl]-2-(4-morpholinyl)-1-propanone and compound (8) in the ratio 92/8

EXAMPLE AI-1

Preparation of a Blue Offset Ink

(9) The following components are mixed (formulation 1): 42.0 g Epoxy acrylate (Ebecryl 2958, provided by Cytec) 22.0 g Tetrafunctional polyester acrylate (Ebecryl 657, provided by Cytec) 3.0 g Propoxylated glycerol triacrylate (Ota 480, provided by Cytec) 7.0 g China clay 1.0 g UV-stabilizer (Florstab UV-1, provided by Kromachem) 17.0 g pigment (IRGALITE Blue GLO, provided by Ciba Inc.)

(10) The photoinitiator mixture of the present invention is added to said formulation 1 as indicated in the following table 2, also listing the test results.

(11) The formulations to be tested are applied using a Prfbau machine onto a corona treated polymeric white foil.

(12) Samples are exposed to a medium pressure mercury lamp (200 W/cm) or a gallium-doted lamp (200 W/cm) under air or nitrogen at different belt speeds: polymerization efficiency is assessed using a REL complete curing tester immediately after the irradiation. In this, an aluminum cylinder over which a fabric is stretched is placed on the printed sample and rotated once around its own axis under a pressure of 220 g/cm.sup.2 in the course of 10 seconds. If visible damage to the sample is caused by this procedure, the printing ink has not cured sufficiently. Reactivity is measured either by the cure speed, defined as the maximum belt speed, required to get proper through cure at a constant light intensity, or by measuring the number of passes at the same belt speed required to get the proper through cure of the ink.

(13) The results are collected in table 2.

(14) TABLE-US-00002 TABLE 2 photoinitiator lamp atmosphere cure speed/passes 3% PM-1 Ga, CM air 4 passes at 20 m/min 3% PM-2 Ga, CM air 2 passes at 20 m/min 3% IRGACURE 369* Ga, CM air 5 passes at 20 m/min 3% PM-2 Ga, CM 500 ppm O.sub.2 90 m/min 2% PM-2 Ga, CM 500 ppm O.sub.2 60 m/min 3% IRGACURE 369* Ga, CM 500 ppm O.sub.2 60 m/min 3% PM-1 Hg, Alu air 70 m/min 2% PM-1 Hg, Alu air 40 m/min 3% IRGACURE 369* Hg, Alu air 40 m/min *= 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]butan-1-one = compound of example 16 CM = cold mirrors Alu = aluminum reflectors

EXAMPLE AI-2

Preparation of a Blue Flexo Ink

(15) The following components are mixed (formulation 2): 15.0 wt.-% hexafunctional polyester acrylate (Ebecryl 450, provided by Cytec) 20.0 wt.-% tetrafunctional polyester acrylate (Ebecryl 812, provided by Cytec) 15.0 wt.-% amine modified polyether acrylate (Ebecryl 83, provided by Cytec) 33.3 wt.-% monofunctional acrylate (Ebecryl 160, provided by Cytec) 0.7 wt.-% silicone additive (DC57, provided by Dow Corning) 16.0 wt.-% pigment (IRGALITE Blue GLO, provided by Ciba Inc.)

(16) The photoinitiator mixture of the present invention is added to said formulation 2 as indicated in the following table 3, also listing the test results.

(17) The testing is performed as described in example A-1, however, the Ga-lamp has either an output of 200 W/cm or 80 W/cm.

(18) TABLE-US-00003 TABLE 3 photoinitiator + 4% DAROCUR 1173** lamp atmosphere cure speed/passes 4% PM-1 Ga, Alu 200 W/cm air 25 m/min 4% PM-2 Ga, Alu 200 W/cm air 30 m/min 4% IRGACURE 369* Ga, Alu 200 W/cm air 20 m/min 4% PM-1 Ga, CM 80 W/cm 500 ppm O.sub.2 3 passes at 200 m/min 4% PM-2 Ga, CM 80 W/cm 500 ppm O.sub.2 4 passes at 200 m/min 4% PM-3 Ga, CM 80 W/cm 500 ppm O.sub.2 3 passes at 200 m/min 4% IRGACURE 369* Ga, CM 80 W/cm 500 ppm O.sub.2 no drying 4% PM-1 Ga, CM 200 W/cm 500 ppm O.sub.2 200 m/min 4% PM-2 Ga, CM 200 W/cm 500 ppm O.sub.2 200 m/min 2% PM-2 Ga, CM 200 W/cm 500 ppm O.sub.2 130 m/min 4% IRGACURE 369* Ga, CM 200 W/cm 500 ppm O.sub.2 130 m/min *= Ciba IRGACURE 369 = 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]butan-1-one = compound of example 16 **= Ciba DAROCUR 1173 = 2-hydroxy-2-methyl-1-phenyl-propan-1-one, provided by Ciba Inc.

EXAMPLE AI-3

Preparation of a Blue Flexo Ink

(19) The photoinitiator mixture to be tested is added to formulation 2 as described in example AI-2. The formulations to be tested are applied using a Prufbau machine (1.4 g/m.sup.2) onto a corona treated polymeric white PEC foil. Samples are exposed to a medium pressure mercury lamp (80 W/cm) equipped with cold mirrors under air at different belt speeds: polymerization efficiency is assessed using a REL complete curing tester immediately after the irradiation. In this, an aluminum cylinder over which a fabric is stretched is placed on the printed sample and rotated once around its own axis under a pressure of 220 g/cm.sup.2 in the course of 10 seconds. If visible damage to the sample is caused by this procedure and the white background is visible, the printing ink has not cured sufficiently. Reactivity is measured by the cure speed, defined as the maximum belt speed, required to get proper through cure at a constant light intensity. The tested photoinitiator mixture and the results are given in table 4.

(20) TABLE-US-00004 TABLE 4 photoinitiator cure speed (m/min) 4% PM-16 120-130 4% IRGACURE 369* 100 *= 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]butan-1-one = compound of example 16, provided by Ciba Inc.

EXAMPLE AI-4

Preparation of a Blue Flexo Ink

(21) The photoinitiator mixture to be tested is added to formulation 2 as described in example AI-2. The formulations to be tested are applied using a Prufbau machine (1.4 g/m.sup.2) onto a corona treated polymeric white PEC foil. Samples are exposed to a medium pressure mercury lamp (80 W/cm) equipped with cold mirrors under nitrogen at different belt speeds: polymerization efficiency is assessed using a REL complete curing tester immediately after the irradiation (as described in example AI-3). In this, an aluminum cylinder over which a fabric is stretched is placed on the printed sample and rotated once around its own axis under a pressure of 220 g/cm.sup.2 in the course of 10 seconds. If visible damage to the sample is caused by this procedure at the surface of the film (color shift), the printing ink has not cured sufficiently. Reactivity is measured by the cure speed, defined as the maximum belt speed, required to get proper through cure at a constant light intensity. The tested photoinitiator mixture and the results are collected in table 5.

(22) TABLE-US-00005 TABLE 5 photoinitiator cure speed (m/min) 4% PM-17 100 4% IRGACURE 379*** 40/50 ***= 2-(4-methylbenzyl)-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]butan-1-one, provided by Ciba Inc.

EXAMPLE AI-5

Preparation of a Blue Flexo Ink

(23) The photoinitiator mixture to be tested is added to formulation 2 as described in example AI-2. The formulations to be tested are applied using a Prufbau machine (1.4 g/m.sup.2) onto a corona treated polymeric white PEC foil. Samples are exposed to a medium pressure mercury lamp (80 W/cm) equipped with cold mirrors under nitrogen at different belt speeds: polymerization efficiency is assessed using a REL complete curing tester immediately after the irradiation. In this, an aluminum cylinder over which a fabric is stretched is placed on the printed sample and rotated once around its own axis under a pressure of 220 g/cm.sup.2 in the course of 10 seconds. If visible damage to the sample is caused by this procedure at the surface of the film (color shift), the printing ink has not cured sufficiently. Reactivity is measured by the cure speed, defined as the maximum belt speed, required to get proper through cure at a constant light intensity. The photoinitiator mixture as well as test results are listed in table 6.

(24) TABLE-US-00006 TABLE 6 photoinitiator + 4% DAROCUR 1173** cure speed (m/min) 4% PM-18 170 4% 2-benzyl-2-(dimethyl-amino)-1-(3,4- 120 dimethoxy-phenyl)-1-butanone **= Ciba DAROCUR 1173 = 2-hydroxy-2-methyl-1-phenyl-propan-1-one, provided by Ciba Inc.

EXAMPLE AI-6

Preparation of a Blue Flexo Ink

(25) The photoinitiator mixture to be tested is added to formulation 2 as described in example AI-2. The formulations to be tested are applied using a Prufbau machine (1.4 g/m.sup.2) onto a corona treated polymeric white PEC foil. Samples are exposed to a medium pressure mercury lamp (80 W/cm) equipped with cold mirrors under nitrogen at different belt speeds: polymerization efficiency is assessed using a REL complete curing tester immediately after the irradiation. In this, an aluminum cylinder over which a fabric is stretched is placed on the printed sample and rotated once around its own axis under a pressure of 220 g/cm.sup.2 in the course of 10 seconds. If visible damage to the sample is caused by this procedure at the surface of the film (color shift), the printing ink has not cured sufficiently. Reactivity is measured by the cure speed, defined as the maximum belt speed, required to get proper through cure at a constant light intensity. The tested mixture as well as the results are collected in table 7.

(26) TABLE-US-00007 TABLE 7 photoinitiator + 4% DAROCUR 1173** cure speed (m/min) 4% PM-19 100 4% IRGACURE 907**** 70 **= Ciba DAROCUR 1173 = 2-hydroxy-2-methyl-1-phenyl-propan-1-one, provided by Ciba Inc. ****= 2-methyl-1-[4-methylthio]phenyl]-2-(4-morpholinyl)-1-propanone, provided by Ciba Inc.

EXAMPLE AE-1

Preparation of Poly(benzylmethacrylate-co-methacrylic acid)

(27) 24 g of benzylmethacrylate, 6 g of methacrylic acid and 0.525 g of azobisisobutyronitrile (AIBN) are dissolved in 90 ml of propylene glycol 1-monomethyl ether 2-acetate (PGMEA). The resulting reaction mixture is placed in a preheated oil bath at 80 C. After stirring for 5 hours at 80 C. under nitrogen, the resulting viscous solution is cooled to room temperature and used without further purification. The solid content is about 25%. The ratio benzylmethacrylate: methacrylic acid is 80:20 by weight.

EXAMPLE AE-2

Preparation of Color Filter Resists (Red, Green and Blue)

(28) Pigment dispersions are prepared by mixing the following components and dispersing them by using a Paint conditioner (SKANDEX).

(29) TABLE-US-00008 Red dispersion 10.0 parts by weight red pigment (PR254, IRGAPHOR RED BT-CF provided by Ciba) 4.0 parts by weight dispersant (Ajisper PB821 provided by Ajinomoto Fine Techno) 10.0 parts by weight solvent, propyleneglycol methyl ether acetate (PGMEA) Green dispersion 6.0 parts by weight green pigment (PG36, Lionel Green 6YK provided by Toyo Ink) 4.0 parts by weight yellow pigment (PY150, CROMOPHTAL Yellow LA2 provided by Ciba) 3.6 parts by weight dispersant (Ajisper PB821 provided by Ajinomoto Fine Techno) 0.4 parts by weight synergist (Solsperse S12000 provided by Lubrizol) 10.0 parts by weight solvent (PGMEA) Blue dispersion 10.0 parts by weight blue pigment (PB15:6, Blue E provided by Toyo Ink) 3.6 parts by weight dispersant (Ajisper PB821 provided by Ajinomoto Fine Techno) 0.4 parts by weight synergist (Solsperse S5000 provided by Lubrizol) 10.0 parts by weight solvent (PGMEA)

(30) Photopolymerizable color filter resists (red, green and blue) are prepared by further adding the following components to the dispersions as described above: 40.0 parts by weight the copolymer of benzylmethacrylate and methacrylic acid (PGMEA solution) according to the above preparation example AE-1 10.0 parts by weight multifunctional acrylate (DPHA, provided by UCB Chemicals)

EXAMPLE AE-3

Resolution Tests of Color Filter Resists

(31) The photoinitiator to be tested is added to the above color filter resist compositions and mixed. The compositions are applied to a glass substrate using an electric applicator with a wire wound bar. The solvent is removed by heating at 80 C. for 10 min in a convection oven. The thickness of the dry film is approximately 2 m. A test negative mask with different sizes of pattern for resolution test (1951 U.S.A.F. test pattern, Edmund) is placed on the resist. Exposure is carried out using a 250 W super high pressure mercury lamp (USHIO, USH-250BY) at a distance of 15 cm. The total exposure dose determined by measuring the light intensity with an optical power meter (ORC UV Light Measure Model UV-MO2 with UV-35 detector) is 50 mJ/cm.sup.2 for the red and green color filter resists 300 mJ/cm.sup.2 for the blue color resist. After exposure, the exposed film is developed with an alkaline solution (5% aqueous solution of DL-A4, Yokohama Yushi) for 80 sec at 28 C. by using a spray type developer (AD-1200, Takizawa Sangyo). The resolution of the initiator system used is characterized by indicating the size of the smallest pattern remained after developing. The smaller the size, the more sensitive is the tested initiator system. The photoinitiator mixtures and the results of the tests are collected in tables 8-10.

(32) TABLE-US-00009 TABLE 8 Red color resist Photoinitiator Resolution/m 2% PM-4 19.7 2% PM-1 19.7 2% PM-5 17.5 2% PM-6 13.9 2% PM-3 12.4 2% PM-7 19.7 2% PM-8 17.5 2% PM-9 15.6 2% PM-10 13.9 2% PM-11 22.1 2% PM-12 17.5 2% PM-13 13.9 2% PM-14 11.0 2% PM-15 11.0 2% IRGACURE 369* 78.7 *= 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]butan-1-one

(33) TABLE-US-00010 TABLE 9 Green color resist Photoinitiator Resolution/m 2% PM-4 8.8 2% PM-1 5.5 2% PM-5 5.0 2% PM-6 5.0 2% PM-3 3.9 2% PM-7 8.8 2% PM-8 5.5 2% PM-9 5.0 2% PM-10 4.4 2% IRGACURE 369 11.0

(34) TABLE-US-00011 TABLE 10 Blue color resist Photoinitiator Resolution/m 4% PM-1 12.4 4% PM-5 12.4 4% PM-6 8.8 4% PM-3 7.0 4% PM-7 15.6 4% PM-8 12.4 4% PM-9 8.8 4% PM-10 8.8 4% IRGACURE 369 >500 (No pattern remained)