Photo-latent titanium catalysts

Abstract

The present invention provides a photolatent Ti-chelate catalyst formulation, comprising (i) at least one compound of the formula (I) wherein R.sub.1 is C.sub.1-C.sub.20alkyl or C.sub.2-C.sub.20alkyl which is interrupted by one or more non-consecutive O-atoms; Y is formula (II) or optionally substituted phenyl; Y.sub.1 is formula (III) or optionally substituted phenyl; Y.sub.2 is formula (IV) or optionally substituted phenyl; Y.sub.3 is formula (V) or optionally substituted phenyl; R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12 and R.sub.13 independently of each other are hydrogen, halogen, optionally substituted C.sub.1-C.sub.20alkyl, or R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12 and R.sub.13 independently of each other are optionally substituted C.sub.6-C.sub.14aryl, provided that only one of R.sub.2, R.sub.3, R.sub.4 is hydrogen and only one of R.sub.5, R.sub.6, R.sub.7 is hydrogen and only one of R.sub.8, R.sub.9, R.sub.10 is hydrogen and only one of R.sub.11, R.sub.12, R.sub.13 is hydrogen; and (ii) at least one chelate ligand compound of the formula IIa, IIb or IIc, wherein Y is formula (VI) or formula (VII); Y.sub.1 is formula (VIII) or formula (IX); R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6 and R.sub.7 independently of each other have on of the meanings as given for R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12 and R.sub.13; and R.sub.14, R.sub.15 and R.sub.16 independently of each other have on of the meanings as given for R.sub.14, R.sub.15 and R.sub.16. ##STR00001##

Claims

1. Ti-chelate catalyst formulation comprising: (i) 95-70% by weight of at least one compound selected from the group consisting of ##STR00063## ##STR00064## ##STR00065## based on the total catalyst formulation; and (ii) at least one chelate ligand compound ##STR00066## wherein 5-30% by weight of at least one chelate ligand is present based on the total catalyst formulation.

2. A polymerizable composition comprising (a) at least one blocked or unblocked isocyanate or isothiocyanate component, (b) at least one polyol; and (c) at least one Ti-chelate catalyst formulation as defined in claim 1.

3. A polymerizable composition according to claim 2, comprising in addition to components (a), (b) and (c), (d) a photosensitizer compound.

4. A method of using the polymerizable composition according to claim 2 comprising: incorporating the polymerizable composition according to claim 2 in adhesives, coatings, sealings, potting components, printing inks, printing plates, foams, moulding compounds, or photostructured layers.

5. A coated substrate coated on at least one surface with a composition according to claim 2.

6. A polymerizable composition comprises (a) at least one blocked or unblocked isocyanate or isothiocyanate component, (b) at least one polyol; and (c) at least one Ti-chelate catalyst formulation as defined in claim 1, which comprises 0.001 to 15% by weight of (c) based on the total composition.

7. A polymerizable composition according to claim 6 comprises 0.01 to 5% by weight of (c) based on the total composition.

8. A process for polymerizing compounds, which are capable to crosslink in the presence of a Lewis acid, characterized in that a Ti-chelate catalyst formulation as defined in claim 1 is added to said compounds and the resulting mixture is irradiated with electromagnetic radiation of a wavelength range of 200-800 nm.

9. A process according to claim 8, wherein the component which is capable to crosslink in the presence of a Lewis acid is a mixture of (a) a blocked or unblocked isocyanate or isothiocyanate component and (b) a polyol.

10. A process according to claim 8 for the preparation of adhesives, sealings, coatings, potting components, printing inks, printing plates, foams, moulding compounds, or photostructured layers.

11. A process for polymerizing compounds, which are capable to crosslink in the presence of a Lewis acid, characterized in that a Ti-chelate catalyst formulation as defined in claim 1 is added to said compounds and the resulting mixture is subjected to a heat treatment, or the mixture is irradiated with electromagnetic radiation of a wavelength range of 200-800 nm and simultaneously with or after the irradiation subjected to a heat treatment.

12. A Ti-chelate catalyst formulation comprising: (i) at least one compound of the formula I ##STR00067## wherein R.sub.1 is C.sub.1-C.sub.8alkyl or C.sub.2-C.sub.12alkyl, which is interrupted by 1-6 non-consecutive O-atoms; Y is ##STR00068## Y.sub.1 is ##STR00069## Y.sub.2 is ##STR00070## Y.sub.3 is ##STR00071## R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12 and R.sub.13 independently of each other are hydrogen, halogen, phenyl or C.sub.1-C.sub.4alkyl, provided that only one of R.sub.2, R.sub.3, R.sub.4 is hydrogen and only one of R.sub.5, R.sub.6, R.sub.7 is hydrogen and only one of R.sub.5, R.sub.9, R.sub.10 is hydrogen and only one of R.sub.11, R.sub.12, R.sub.13 is hydrogen; or R.sub.5 and R.sub.6, and/or R.sub.5 and R.sub.9, together with the C-atom to which they are attached form a 5 or 6 membered saturated ring, R.sub.14, R.sub.15 and R.sub.16 independently of each other are hydrogen, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, benzoyl, nitro or NR.sub.17R.sub.18; or R.sub.14 and R.sub.15 together with the phenyl ring to which they are attached form thioxanthyl which is unsubstituted or is substituted by C.sub.1-C.sub.4alkyl; R.sub.17 and R.sub.15 are C.sub.1-C.sub.4alkyl; and (ii) at least one chelate ligand compound ##STR00072## wherein (i) 95-70% by weight of at least one compound of the formula I, and (ii) 5-30% by weight of at least one chelate ligand compound are present based on the total catalyst formulation.

Description

PREPARATION EXAMPLES

Catalyst 1: Preparation of

(1) ##STR00030##

(2) The compound is prepared as described in WO2009/050115, example 55.

Catalyst 2: Preparation of

(3) ##STR00031##

(4) In a 25 ml dry three-neck-flask 1.44 g (4.2 mmol) of Ti(IV) butoxide are dissolved in 5 ml dry dichloromethane under argon. 1.98 g (8.4 mmol) of 4,4-dimethyl-1-(4-methoxyphenyl)pentane-1,3-dione (prepared as described in WO2009/050115, example 52.1) are added in the course of 15 min at room temperature. The reaction mixture is then evaporated and dried under reduced pressure to give 2.58 g of the title compound as yellow oil. The structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3). [ppm]: 0.78-1.59 (32H), 3.80-3.88 (6H), 4.42 (4H), 6.24-6.34 (2H), 6.73-6.70 (4H), 7.69-8.01 (4H).

Catalyst 3: Preparation of

(5) ##STR00032##

(6) In a 100 ml dry three-neck-flask 17.3 g (61 mmol) Ti(VI) isopropoxide are dissolved in 45 ml dry 2-propanol under argon. 25.0 g (122 mmol) of 4,4-dimethyl-1-phenylpentane-1,3-dione are added slowly in the course of 30 min at room temperature. After 2 h the reaction flask is cooled in an ice-bath and the resulting white precipitate filtered off. The filter cake is washed with 2-propanol and then dried under reduced pressure to give 26.9 g (77%) of the title product as a white solid. The structure is confirmed by .sup.1H-NMR spectrum. M.p. 107-109 C.

Catalyst 4: Preparation of

(7) ##STR00033##

(8) The compound is prepared as described above for catalyst 3, but using 4,4-dimethyl-1-(3,4-dimethoxyphenyl)pentane-1,3-dione as chelate ligand. Yellowish solid; M.p. 117-118 C.

Catalyst 5: Preparation of

(9) ##STR00034##

(10) The compound is prepared as described above for catalyst 3, but using 4,4-dimethyl-1-(2,4,6-trimethylphenyl)pentane-1,3-dione as chelate ligand. The product does not precipitate from the reaction mixture and is isolated by removal of the solvent under reduced pressure and subsequent drying under vacuum. Orange resin; .sup.1H-NMR (CDCl.sub.3), [ppm]: 1.05-1.29 (m, 30H), 2.19-2.38 (m, 18H), 4.73-4.88 (m, 2H), 5.76/5.79 (2 s, 2H), 6.78/6.87 (2 s, 4H).

Catalyst 6: Preparation of

(11) ##STR00035##

(12) The compound is prepared as described above for catalyst 5, but using 4,4-dimethyl-1-(4-dimethylamino-phenyl)pentane-1,3-dione as chelate ligand. Orange solid; M.p. 69-73 C.

Catalyst 7 (CAS 144665-26-9)

(13) ##STR00036##

(14) The catalyst is commercially available from ABCR.

Catalyst 8 Preparation of

(15) ##STR00037##

(16) The compound is prepared as described above for catalyst 3, but using 4-methyl-1-phenylpentane-1,3-dione as chelate ligand. White solid; M.p. 86.5-89 C.

Catalyst 9 Preparation of

(17) ##STR00038##

(18) The preparation is done according to the literature procedure published in Bull. Korean Chem. Soc. 1996, 17(7), 637.

Catalyst 10 Preparation of

(19) ##STR00039##

(20) The compound is prepared as described above for catalyst 5, but using 1,1,1-trifluoro-5,5-dimethyl-hexane-2,4-dione as chelate ligand. Yellow oil, partially crystalline. .sup.1H-NMR (CDCl.sub.3), [ppm]: 0.95-1.26 (30H), 4.67-4.75 (2H), 6.06-6.10 (2H).

Catalyst 11 Preparation of

(21) ##STR00040##

(22) The compound is prepared as described above for catalyst 3, but using 4,4,4-trifluoro-1-phenyl-butane-1,3-dione as chelate ligand. White solid; M.p. 77-79.5 C.

Catalyst 12 Preparation of

(23) ##STR00041##

(24) In a 100 ml dry three-neck-flask 6.00 g (10.5 mmol) of Catalyst 3 are suspended in 60 g of anhydrous t-butyl-alcohol. The reaction mixture is heated to give a clear solution and the solvent is distilled off under atmospheric pressure to give a white solid. After drying under vacuum, 6.29 g of the title compound is obtained as white powder. The structure is confirmed by .sup.1H-NMR spectroscopy. M.p. 165-167 C.

Catalyst 13 Preparation of

(25) ##STR00042##

(26) In a 5 ml glass flask 1.0 g (1.7 mmol) of Catalyst 3 and 0.25 g (1.2 mmol) of 4,4-dimethyl-1-(4-methoxy-phenyl)pentane-1,3-dione are heated to 80 C. until an orange clear resin is obtained. The product is confirmed to be a homogenous mixture of the two compounds by .sup.1H-NMR spectrum in CDCl.sub.3.

Catalyst 14 Preparation of

(27) ##STR00043##

(28) In a 5 ml glass flask 1.0 g (1.7 mmol) of Catalyst 3 and 1.0 g (4.9 mmol) of 4,4-dimethyl-1-(4-methoxy-phenyl)pentane-1,3-dione are heated to 60 C. until an orange clear liquid is obtained. The product is confirmed to be a homogenous mixture of the two compounds by .sup.1H-NMR spectrum in CDCl.sub.3.

Catalyst 15 Preparation of

(29) ##STR00044##

(30) The compound was prepared as described above for catalyst 5, but using 4,4-dimethyl-1-phenyl-hexane-1,3-dione as chelate ligand. Yellowish oil. .sup.1H-NMR (CDCl.sub.3), [ppm]: 0.54-1.75 (m, 34H), 4.76-4.85 (m, 2H), 6.28/6.33 (2 s, 2H), 7.29-7.49 (m, 6H), 7.72-7.75/8.00-8.03 (2 m, 4H).

Preparation of 1,3-Diketone Ligands 1-5

(31) Preparation of 1,3-diketone ligands is done as described in Organic Letters 2007, 21, 4139-4142, starting from the corresponding carboxylic acid and methylketone reactants via the benzotriazole amide intermediate.

(32) TABLE-US-00001 Starting M.p. .sup.1H-NMR in CDCl.sub.3 Ligand materials Aspect Yield [ C.] [ppm] 3,3-dimethyl-2- butanone; 1-methyl-cyclo- hexane- carboxylic acid acid yellow oil 64% Enol tautomer: 1.12 (s, 3H), 1.18 (s, 9H); 1.31-1.56 (m, 8H); 1.88-1.94 (m, 2H); 5.75 (s, 1H) acetophenone; 1-phenyl-cyclo- pentane- carboxylic acid yellow solid 77% 114-120 acetophenone; 1-methyl-cyclo- hexane- carboxylic acid orange oil 90% Enol tautomer: 1.19 (s, 3H); 1.35-1.61 (m, 8H); 1.99-2.04 (m, 2H); 6.33 (s, 1H); 7.43-7.53 (m, 3H) 7.87-7.90 (m, 2H) 3,3-dimethyl-2- butanone; benzophenone- 4-carboxylic acid white solid 49% 67-76 3,3-dimethyl-2- butanone; 1- phenyl- cyclopentane- carboxylic acid white solid 70% 45-47

Catalyst 16 Preparation of

(33) ##STR00050##

(34) The compound is prepared as described above for catalyst 2, but using ligand 1 as chelate ligand. Yellow oil; .sup.1H-NMR (CDCl.sub.3), [ppm]: 0.81-2.13 (m, 58H), 4.21-4.34 (m, 4H), 5.81 (s, 2H).

Catalyst 17 Preparation of

(35) ##STR00051##

(36) The compound is prepared as described above for catalyst 2, but using ligand 2 as chelate ligand. Orange oil; .sup.1H-NMR (CDCl.sub.3), [ppm]: 0.77-2.74 (m, 30H), 4.39-4.61 (m, 4H), 6.06/6.20 (2 s, 2H), 6.88-7.97 (m, 20H).

Catalyst 18 Preparation of

(37) ##STR00052##

(38) In a 25 ml three-neck-flask 0.8 g (2.81 mmol) of Ti(IV) isopropoxide are dissolved in 10 ml toluene under argon. 1.38 g (5.63 mmol) of ligand 3 are added at room temperature. After 2 h, 1.25 g (16.9 mmol) tert-butyl-alcohol are added and the reaction mixture is heated to reflux, then the solvent is evaporated and the residue dried under reduced pressure to give 1.6 g (87%) of the title compound as orange resin. The structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3, [ppm]): 0.93-1.60 (m, 40H); 1.87-1.91 (m, 2H); 2.19-2.22 (m, 2H); 6.27-6.33 (m, 2H); 7.33-7.46 (m, 6H); 7.71-7.76 (m, 2H); 7.91-8.00 (m, 2H).

Catalyst 19 Preparation of

(39) ##STR00053##

(40) The compound is prepared as described above for catalyst 18, but using ligand 4 as chelate ligand. Yellow resin; .sup.1H-NMR (CDCl.sub.3), [ppm]: 1.03-1.33 (m, 36H); 6.32 (s, 2H); 7.43-8.08 (m, 18H).

Catalyst 20 Preparation of

(41) ##STR00054##

(42) The compound is prepared as described above for catalyst 5, but using ligand 5 as chelate ligand. Colorless resin. .sup.1H-NMR (CDCl.sub.3), [ppm]: 0.84-1.20 (m, 30H), 1.45-2.70 (m, 16H), 4.50-4.65 (m, 2H), 5.50-5.60 (m, 2H), 7.12-7.47 (m, 10H).

Catalyst 21 Preparation of

(43) ##STR00055##

(44) The compound is prepared as described above for catalyst 3, but using 4,4-dimethyl-1-(4-nitrophenyl)pentane-1,3-dione as chelate ligand. Yellowish solid; M.p. 139-143 C.

Preparation of Catalyst 22

22a) 7-Methyl-thioxanthene-9-one-3-carboxylic acid 1,1-dimethyl-propyl ester

(45) ##STR00056##

(46) 7.0 g (25.9 mmol) of 7-Methyl-thioxanthene-9-one-3-carboxylic acid is added to 20 ml thionylchloride and the suspension is heated to reflux during 5 h. The excess of thionylchloride is distilled off, the residue cooled to 0 C., dissolved in 30 ml of DMF, then 11.4 g (103.6 mmol) of sodium-tert-pentoxide is slowly added. The reaction mixture is poured into ice-water and the product is extracted with ethylacetate. The solvent is evaporated under reduced pressure and the crude product purified by chromatography over silica gel using toluene as eluent to yield 1.8 g (20%) of title compound as a yellow solid. The structure is confirmed by .sup.1H-NMR spectra. M.p. 114-116 C.

22b) Ligand 6

(47) ##STR00057##

(48) 0.54 g (5.3 mmol) of 3,3-dimethyl-2-butanone is added to a solution of 0.62 g (5.3 mmol) of potassium-tert-butoxide in 10 ml of DMF at 0 C. 1.5 g (4.41 mmol) of 7-methyl-thioxanthene-9-one-3-carboxylic acid 1,1-dimethyl-propyl ester is added, the reaction mixture stirred for 4 h at 25 C., then poured into 10 ml of ice-water containing 10 ml concentrated aq. HCl. Extraction with toluene and evaporation of the solvent gives the crude product which is purified by chromatography over silica gel using toluene as eluent to yield 0.56 g (36%) of the title compound as a yellow solid. The structure is confirmed by .sup.1H-NMR spectra. M.p.: 198-203 C.

22c) Catalyst 22

(49) ##STR00058##

(50) The compound is prepared as described above for catalyst 3, but using ligand 6 as chelate ligand. Yellow solid; M.p. 160-164 C.

Catalyst 23 Preparation of

(51) ##STR00059##

(52) 1.08 g (1.9 mmol) of catalyst 3 is dissolved under argon in 20 ml of absolute toluene. The clear solution is stirred at room temperature and 0.46 g (3.8 mmol) of 2-(2-methoxyethoxy)ethanol are slowly added during 15 minutes. 2-Propanol is removed by azeotropic distillation at 60 C. under reduced pressure (80 mbar) during 2 hours. The solvent is then completely removed under reduced pressure to give 1.24 g (94%) of the title product as a yellow solid. The structure is confirmed by .sup.1H-NMR spectrum. M.p. 166-210 C.

Preparation of Catalyst 24

24a) Ligand 7

(53) ##STR00060##

(54) The compound is prepared as described above for ligand 6 from methyl 3,5-dimethoxybenzoate and 3,3-dimethyl-2-butanone. Yellow solid; .sup.1H-NMR (CDCl.sub.3), [ppm]: 1.24 (s, 9H), 3.83 (s, 6H), 6.24 (s, 1H), 6.61 (d, 1H), 7.02 (d, 2H).

24b) Catalyst 24

(55) ##STR00061##

(56) The compound is prepared as described above for catalyst 5, but using ligand 7 as chelate ligand. Orange solid. M.p. 99-102 C.

APPLICATION EXAMPLES

(57) The following commercially available 1,3-diketones are used:

(58) ##STR00062##

(59) Curing and Pot-Life of a Two Packs Polyurethane System Based on a Polyacrylic Polyol and an aliphatic polyisocyanate:

(60) The polyurethane is the reaction product of two basic components: a polyol (Component A) and a polyisocyanate (Component B). An organometallic photolatent catalyst is added to the total composition of A and B in order to speed up the reaction of A with B.

(61) In the following examples Component A includes all ingredients other than the polyisocyanate. The photolatent catalyst and the 1,3 diketone are dissolved carefully into Component A prior to the addition of Component B.

Component A1

(62) TABLE-US-00002 73.1 parts of a polyol (Desmophen A VP LS 2350; Bayer AG) 0.9 parts of a flow improver (Byk 355; Byk-Chemie) 0.7 parts of a defoamer (Byk 141 ; Byk-Chemie) 0.7 parts of a flow improver (Byk 333; Byk-Chemie) 24.6 parts of xylene/methoxypropylacetate/butylacetate (1/1/1)

Component B1

(63) Aliphatic polyisocyanate [(HDI-Trimer) Desmodur N3390 BA; Bayer AG]

(64) The basic testing formulations are composed of:

(65) TABLE-US-00003 7.52 parts of component A1 2.00 parts of component B1

Example A1

(66) The testing samples are prepared by adding 1,3-diketones (ligands) and 0.025% weight of Metal (on solid) of photolatent catalysts. The amount of ligand is adjusted to have the following weight ratios between the organometallic photolatent catalyst and ligand: 70/30, 80/20 and 90/10.

(67) After preparation, the mixtures are stored in the dark at room temperature. The potlife of each formulation is monitored by measuring the viscosity at 25 C. by the mean of a viscometer from Epprecht Instruments+Control AG. The measurements are done after the preparation of formulation and each hour until 7 h. The viscosity increases with the time. The lower the increase of the viscosity, the longer is the potlife of the formulation and consequently the larger is the working window. The catalysts and ligands which are used in the experiment as well as results are presented in the following table 1.

(68) TABLE-US-00004 TABLE 1 Viscosity at 25 C. (poises) Catalysts Ratio 0 h 1 h 2 h 3 h 4 h 5 h 6 h 7 h No catalyst 0.6 0.6 1.2 1.7 2.2 2.2 2.4 2.5 Catalyst 3 1.8 5.8 16.6 gelled gelled gelled gelled gelled Catalyst 3/ 70/30 1.4 2.3 2.8 3.8 5.1 6.5 8.6 9.6 CAS 1118-71-4 Catalyst 3/ 80/20 1.5 3 4 5.6 8.4 13 24 44.8 CAS 1118-71-4 Catalyst 3/ 90/10 1.9 3.2 5.3 9.3 16.4 gelled gelled gelled CAS 1118-71-4 Catalyst 3/ 70/30 1.8 2.8 3.3 3.8 5.3 8.6 8.8 12.2 CAS 18362-64-6 Catalyst 3/ 80/20 1.7 2.8 4.5 5.4 10 18 19.8 31.6 CAS 18362-64-6 Catalyst 3/ 90/10 2 3.6 9.3 13 29.6 gelled gelled gelled CAS 18362-64-6 Catalyst 3/ 70/30 0.8 1.2 2.8 5.4 11.8 13 16.4 32 CAS 120-46-7 Catalyst 3/ 80/20 1 1.6 3.5 6.9 14.4 24.4 48 gelled CAS 120-46-7 Catalyst 3/ 90/10 0.8 2.8 3.6 12.4 18.4 39.6 gelled gelled CAS 120-46-7 Catalyst 3/ 70/30 1.4 2.4 3.2 4.2 5.9 8 11.8 14 CAS 13988-67-5 Catalyst 3/ 80/20 1.5 3 4.2 5.8 9.1 14.6 27.2 gelled CAS 13988-67-5 Catalyst 3/ 90/10 1.8 4.2 6.4 9.4 22.4 gelled gelled gelled CAS 13988-67-5 Catalyst 3/ 70/30 1.2 2 2 3 3.4 3.8 4.7 5.2 CAS 22767-90-4 Catalyst 3/ 80/20 1.4 2.6 3.4 10.4 11.4 15.2 gelled gelled CAS 22767-90-4 Catalyst 3/ 90/10 1.3 3.2 5.8 17.6 27.2 gelled gelled gelled CAS 22767-90-4

Example A2

(69) The testing samples are prepared by adding 1,3-diketones (ligands) and 0.025% weight of Metal (on solid) of photolatent catalysts. The amount of ligand is adjusted to have the following ratios between the organometallic photolatent catalyst and ligand: 70/30, 80/20 and 90/10.

(70) The mixtures are applied with a 76 m split coater on two glass plates of 30 cm length. One plate is irradiated using a UV processor from IST Metz (mercury lamps, 2*100 m) at a belt speed of 5 m/min, whereas a second one is not irradiated. The reactivity of the mixtures is determined by measuring the tack free time. Therefore the samples are set up on a drying recorder from ByK Gardner, where a needle is moving with a constant speed over the coated substrate for 24 h. The recording is carried out in the dark, at room temperature. The tack free time is the period of time needed for the sample to cure in such a manner that no tack is left on the surface upon touch of the needle in the recorder.

(71) The potlife of the formulation is visually monitored at room temperature. In fact, the time when the formulation is gelled in the flask, is determined.

(72) The lower the value of the tack free time, the faster is the reaction of the polyol with the isocyanate.

(73) The higher the difference between the value of the tack free time of the irradiated sample and the non-irradiated sample (with a tack free value of the irradiated sample, which is lower than the one of the non-irradiated one), the more photolatent is the catalyst.

(74) The higher the value of potlife, the more stable is the mixture in the flask.

(75) The catalysts which are used in the test as well as the results are collected in the following table 2.

(76) TABLE-US-00005 TABLE 2 Tack free time (stage3/4) h 2*100 W Catalysts Ratio Gelled time No irradiation 5 m/min No catalyst >24 h Catalyst 3 2 < h < 3 6.5 2.5 Catalyst 3/ 70/30 7 < h < 24 7.5 5 CAS 1118-71-4 Catalyst 3/ 80/20 7 < h < 24 7 3.5 CAS 1118-71-4 Catalyst 3/ 90/10 4 < h < 5 8 2.5 CAS 1118-71-4 Catalyst 3/ 70/30 7 < h < 24 8 6.5 CAS 18362-64-6 Catalyst 3/ 80/20 7 < h < 24 9 4.5 CAS 18362-64-6 Catalyst 3/ 90/10 4 < h < 5 9 4 CAS 18362-64-6 Catalyst 3/ 70/30 7 < h < 24 9.5 5.5 CAS 120-46-7 Catalyst 3/ 80/20 6 < h < 7 9 3.5 CAS 120-46-7 Catalyst 3/ 90/10 5 < h < 6 6.5 3.5 CAS 120-46-7 Catalyst 3/ 70/30 7 < h < 24 9 4.5 CAS 13988-67-5 Catalyst 3/ 80/20 6 < h < 7 7.5 4 CAS 13988-67-5 Catalyst 3/ 90/10 4 < h < 5 6 2 CAS 13988-67-5 Catalyst 3/ 70/30 7 < h < 24 10 5.5 CAS 22767-90-4 Catalyst 3/ 80/20 5 < h < 6 8.5 5 CAS 22767-90-4 Catalyst 3/ 90/10 4 < h < 5 8 4 CAS 22767-90-4 Catalyst 14/ 7 < h < 24 15 11.5 0.125% benzophenone (DAROCUR from BASF SE)

Example A3

(77) The testing samples are prepared by adding 1,3-diketones (ligands) and 0.025% weight of Metal (on solid) of photolatent catalysts. The amount of ligand is adjusted to have the following weight ratios between the organometallic photolatent catalyst and ligand: 70/30, 80/20 and 90/10.

(78) After preparation, the mixtures are stored in the dark at room temperature. The potlife of each formulation is monitored by measuring the viscosity at 25 C. by the mean of a viscometer from Epprecht Instruments+Control AG. The measurements are done after the preparation of formulation and each hour until 7 h. The viscosity increases with the time. The lower the increase of the viscosity, the longer is the potlife of the formulation and consequently the larger is the working window. The catalysts and ligands which are used in the experiment as well as results are presented in the following table 3.

(79) TABLE-US-00006 TABLE 3 Viscosity at 25 C. (poises) Catalysts Ratio 0 h 1 h 2 h 3 h 4 h 5 h 6 h 7 h No catalyst 1.2 1.8 1.8 2 2 2.4 2.6 3 Catalyst 7 1.4 4.8 10.8 16 gelled gelled gelled gelled Catalyst 7/ 70/30 1.4 2.4 3 3.8 4.8 6 7.4 8.8 CAS 18362-64-6 Catalyst 7/ 80/20 1.6 2.6 3.6 5.2 7.2 11.2 16 20 CAS 18362-64-6 Catalyst 7/ 90/10 1.6 4.4 8.4 19.2 24 gelled gelled gelled CAS 18362-64-6 Catalyst 7/ 70/30 1.4 2.6 4.2 6 10.4 14.4 20 gelled CAS 120-46-7 Catalyst 7/ 80/20 1.6 3.4 5.6 10 17.6 24 gelled gelled CAS 120-46-7 Catalyst 7/ 90/10 1.6 4 8.2 19.2 20 gelled gelled gelled CAS 120-46-7

Example A4

(80) The testing samples are prepared by adding 1,3-diketones (ligands) and 0.025% weight of Metal (on solid) of photolatent catalysts. The amount of ligand is adjusted to have the following ratios between the organometallic photolatent catalyst and ligand: 70/30, 80/20 and 90/10.

(81) The mixtures are applied with a 76 m split coater on two glass plates of 30 cm length. One plate is irradiated using a UV processor from IST Metz (mercury lamps, 2*100 m) at a belt speed of 5 m/min, whereas a second one is not irradiated. The reactivity of the mixtures is determined by measuring the tack free time. Therefore the samples are set up on a drying recorder from ByK Gardner, where a needle is moving with a constant speed over the coated substrate for 24 h. The recording is carried out in the dark, at room temperature. The tack free time is the period of time needed for the sample to cure in such a manner that no tack is left on the surface upon touch of the needle in the recorder.

(82) The potlife of the formulation is visually monitored at room temperature. In fact, the time when the formulation is gelled in the flask, is determined.

(83) The lower the value of the tack free time, the faster is the reaction of the polyol with the isocyanate.

(84) The higher the difference between the value of the tack free time of the irradiated sample and the non-irradiated sample (with a tack free value of the irradiated sample, which is lower than the one of the non-irradiated one), the more photolatent is the catalyst.

(85) The higher the value of potlife, the more stable is the mixture in the flask.

(86) The catalysts which are used in the test as well as the results are collected in the following table 4.

(87) TABLE-US-00007 TABLE 4 Tack free time (stage3/4) h 2*100 W Catalyst Ratio Gelled time No irradiation 5 m/min No catalyst >24 h Catalyst 7 3 < h < 4 6 1.5 Catalyst 7/ 70/30 7 < h < 24 7.5 5.5 CAS 18362-64-6 Catalyst 7/ 80/20 7 < h < 24 6.5 3 CAS 18362-64-6 Catalyst 7/ 90/10 4 < h < 5 6 2 CAS 18362-64-6 Catalyst 7/ 70/30 6 < h < 7 5 3.2 CAS 120-46-7 Catalyst 7/ 80/20 5 < h < 6 5 2 CAS 120-46-7 Catalyst 7/ 90/10 4 < h < 5 4.2 1.5 CAS 120-46-7

Example A5

(88) The testing samples are prepared by adding 1,3-diketones (ligands) and 0.025% weight of Metal (on solid) of photolatent catalysts. The amount of ligand is adjusted to have the following weight ratios between the organometallic photolatent catalyst and ligand: 70/30, 80/20 and 90/10.

(89) After preparation, the mixtures are stored in the dark at room temperature. The potlife of each formulation is monitored by measuring the viscosity at 25 C. by the mean of a viscometer from Epprecht Instruments+Control AG. The measurements are done after the preparation of formulation and each hour until 7 h. The viscosity increases with the time. The lower the increase of the viscosity, the longer is the potlife of the formulation and consequently the larger is the working window. The catalysts and ligands which are used in the experiment as well as results are presented in the following table 5.

(90) TABLE-US-00008 TABLE 5 Viscosity at 25 C. (poises) Catalysts Ratio 0 h 1 h 2 h 3 h 4 h 5 h 6 h 7 h No catalyst 1.6 1.8 1.8 2 2.4 2.6 2.8 3 Catalyst 8 2 4.8 8.8 12.4 25 gelled gelled gelled Catalyst 8/ 70/30 1.8 2.4 3.2 3.8 5.2 6.2 8.4 15.6 CAS 18362-64-6 Catalyst 8/ 80/20 2 3.2 4.2 5.2 8.8 12.4 21.6 27 CAS 18362-64-6 Catalyst 8/ 90/10 2 3.6 5.6 6.6 12 20 32 gelled CAS 18362-64-6 Catalyst 8/ 70/30 1.8 4 4.4 5 8.4 12 17.6 22 CAS 120-46-7 Catalyst 8/ 80/20 2 4.2 5.8 10 18.6 23.2 33 gelled CAS 120-46-7 Catalyst 8/ 90/10 2 4.4 7.6 10 22.4 33 gelled gelled CAS 120-46-7

Example A6

(91) The testing samples are prepared by adding 1,3-diketones (ligands) and 0.025% weight of Metal (on solid) of photolatent catalysts. The amount of ligand is adjusted to have the following ratios between the organometallic photolatent catalyst and ligand: 70/30, 80/20 and 90/10.

(92) The mixtures are applied with a 76 m split coater on two glass plates of 30 cm length. One plate is irradiated using a UV processor from IST Metz (mercury lamps, 2*100 m) at a belt speed of 5 m/min, whereas a second one is not irradiated. The reactivity of the mixtures is determined by measuring the tack free time. Therefore the samples are set up on a drying recorder from ByK Gardner, where a needle is moving with a constant speed over the coated substrate for 24 h. The recording is carried out in the dark, at room temperature. The tack free time is the period of time needed for the sample to cure in such a manner that no tack is left on the surface upon touch of the needle in the recorder.

(93) The potlife of the formulation is visually monitored at room temperature. In fact, the time when the formulation is gelled in the flask, is determined.

(94) The lower the value of the tack free time, the faster is the reaction of the polyol with the isocyanate.

(95) The higher the difference between the value of the tack free time of the irradiated sample and the non-irradiated sample (with a tack free value of the irradiated sample, which is lower than the one of the non-irradiated one), the more photolatent is the catalyst.

(96) The higher the value of potlife, the more stable is the mixture in the flask.

(97) The catalysts which are used in the test as well as the results are collected in the following table 6.

(98) TABLE-US-00009 TABLE 6 Tack free time (stage3/4) h 2*100 W Catalyst Ratio Gelled time No irradiation 5 m/min No catalyst >24 h Catalyst 8 4 < h < 5 4.2 2 Catalyst 8/ 70/30 7 < h < 24 6.2 3.7 CAS 18362-64-6 Catalyst 8/ 80/20 7 < h < 24 5.5 2.5 CAS 18362-64-6 Catalyst 8/ 90/10 6 < h < 7 5 2.5 CAS 18362-64-6 Catalyst 8/ 70/30 7 < h < 24 5.5 3.5 CAS 120-46-7 Catalyst 8/ 80/20 6 < h < 7 6 2.5 CAS 120-46-7 Catalyst 8/ 90/10 5 < h < 6 4.5 2.2 CAS 120-46-7

Example A7

(99) The testing samples are prepared by adding the Ti catalyst and 1,3-diketone additive to 7.52 g of component A1 of the basic testing formulation of example A1. After mixing the component A1 with 2.0 g of component B1, the visual pot-life of the formulation (time where no change in viscosity is visible), the time to considerable viscosity, and the time to high viscosity are observed.

(100) The catalysts and additives which are used in the test as well as the results of the tests are collected in the following table 7.

(101) TABLE-US-00010 TABLE 7 Considerably Highly Visual Pot- viscous viscous Catalyst/(g) Additive/(g) life (min.) (min.) (min.) >600 >3000 Catalyst 1/ 70 110 130 0.075 Catalyst 1/ CAS 1118-71- 210 450 660 0.075 4/0.019 Catalyst 2/ 50 90 120 0.083 Catalyst 2/ CAS 120-46- 180 400 480 0.083 7/0.021 Catalyst 4/ 50 100 120 0.087 Catalyst 4/ CAS 13988-67- 230 360 450 0.087 5/0.022 Catalyst 5/ 90 200 350 0.082 Catalyst 5/ CAS 1118-71- 360 840 1200 0.082 4/0.021 Catalyst 6/ 50 80 100 0.083 Catalyst 6/ CAS 120-46- 120 210 240 0.083 7/0.021 Catalyst 9/ 60 180 240 0.077 Catalyst 9/ CAS 18362-64- 360 600 720 0.077 6/0.019 Catalyst 10/ 120 240 320 0.070 Catalyst 10/ CAS 120-46-7/ 900 1320 1560 0.070 0.017 Catalyst 11/ 60 180 300 0.075 Catalyst 11/ CAS 1118-71-4 600 1020 1140 0.075 /0.019 Catalyst 12/ 80 120 140 0.075 Catalyst 12/ CAS 18362-64- 300 480 680 0.075 6/0.019 Catalyst 15/ 60 120 170 0.075 Catalyst 15/ CAS 13988-67- 360 480 600 0.075 5/0.022 Catalyst 23/ 90 150 170 0.087 Catalyst 23/ CAS 18362-64- 300 540 600 0.087 6/0.022

Example A 8

(102) The testing samples are prepared by adding photolatent metal catalysts, 0.025% weight of metal and 1,3-diketones (ligands). to 7.52 g of component A1 of the basic testing formulation of example A1. The amount of ligand is adjusted to have the following weight ratios between the organometallic photolatent catalyst and the ligand: 70/30, 80/20 and 90/10.

(103) After the mixture of the component A1 with 2 g of component B1, the mixtures are stored in the dark at room temperature. The potlife of each formulation is monitored by measuring the viscosity at 25 C. by means of a viscometer from Epprecht Instruments+Control AG. The measurements are done after the preparation of formulation and each hour until 7 h. The viscosity increases with the time. The lower the increase of the viscosity, the better is the potlife of the formulation and consequently the larger is the working window. The catalysts and ligands which are used in the experiment as well as results are presented in the following table 8.

(104) TABLE-US-00011 TABLE 8 Viscosity at 25 C. (poises) Catalysts Ratio 0 h 1 h 2 h 3 h 4 h 5 h 6 h 7 h Catalyst 3/ 70/30 1.5 2.6 3.8 5.8 7.8 15 24 32 Ligand 7 Catalyst 3/ 80/20 1.4 2.6 5.1 6.8 11.2 22 32 gelled Ligand 7 Catalyst 3/ 90/10 1.5 3.3 6.7 11.6 21 gelled gelled gelled Ligand 7 Catalyst 3/ 70/30 1.5 1.9 2.4 3.3 4 5.3 6.4 7.2 Ligand 3 Catalyst 3/ 80/20 1.3 2.1 3.3 4.9 6.6 12 19 21 Ligand 3 Catalyst 3/ 90/10 1.5 2.4 4.5 7 11.6 26 48 gelled Ligand 3 Catalyst 18- 1.6 3.1 5.8 7.7 15.2 40 gelled gelled without ligand Catalyst 18/ 70/30 1.3 1.9 2.3 2.6 3.2 3.5 4.5 5.5 Ligand 3 Catalyst 18/ 80/20 1.5 2.2 2.6 3.9 4.6 5.4 7 11.2 Ligand 3 Catalyst 18/ 90/10 1.6 2.4 3.5 4.7 6.8 8.4 11.6 19 Ligand 3 Catalyst 18/ 70/30 1.4 2.2 2.7 3 3.8 4.3 6 7.7 Ligand 7 Catalyst 18/ 80/20 1.6 2.4 3 3.8 5.1 6.4 8.6 11.2 Ligand 7 Catalyst 18/ 90/10 1.6 2.5 4 5.1 6.8 8.6 14 19 Ligand 7 Catalyst 18/ 70/30 1.4 2.1 2.3 2.8 3.6 4.1 4.8 5.6 CAS 1118-71-4 Catalyst 18/ 80/20 1.6 2.2 2.7 3.4 4.4 5.6 7.6 8.2 CAS 1118-71-4 Catalyst 18/ 90/10 1.8 2.2 3.2 4.3 6.7 7.6 13.6 18 CAS 1118-71-4 Catalyst 24 1.6 4.1 8.6 14 36 gelled gelled gelled without ligand Catalyst 24/ 70/30 1.2 1.9 2.7 3.4 4 4.8 7 9.3 Ligand 3 Catalyst 24/ 80/20 1.3 2.2 3.1 4.2 5.9 8.2 11.4 19 Ligand 3 Catalyst 24/ 90/10 1.4 2.4 3.8 6.2 8 12 18 36 Ligand 3 Catalyst 24/ 70/30 1.3 1.9 2.6 3.1 3.7 4.6 6.1 8.5 Ligand 7 Catalyst 24/ 80/20 1.3 2.1 3.5 5.2 5.8 8.1 12.4 26 Ligand 7 Catalyst 24/ 90/10 1.4 2.3 3.9 6.4 9 14 24 gelled Ligand 7 Catalyst 24/ 70/30 1.4 2 2.4 3.2 3.5 4.4 5.8 6.9 CAS 1118-71-4 Catalyst 24/ 80/20 1.4 2.1 2.8 4 5 6.4 8.2 12 CAS 1118-71-4 Catalyst 24/ 90/10 1.5 2.5 3.9 7 8.3 17 27 gelled CAS 1118-71-4

Example A 9

(105) The testing samples are prepared by adding photolatent metal catalysts 0.025% weight of metal and 1,3-diketones (ligands) to 7.52 g of component A1 of the basic testing formulation of example A1. The amount of ligand is adjusted to have the following weight ratios between the organometallic photolatent catalyst and ligand: 70/30, 80/20 and 90/10.

(106) After the mixture of the component A1 with 2 g of component B1, the mixtures are applied with a 76 m split coater on two glass plates of 30 cm length. One plate is irradiated using a UV processor from IST Metz (mercury lamps, 2*100 m) at a belt speed of 5 m/min, whereas a second one is not irradiated. The reactivity of the mixtures is determined by measuring the tack free time. Therefore the samples are set up on a drying recorder from ByK Gardner, where a needle is moving with a constant speed over the coated substrate for 24 h. The recording is carried out in the dark, at room temperature. The tack free time is the period of time needed for the sample to cure in such a manner that no tack is left on the surface upon touch of the needle in the recorder.

(107) The lower the value of the tack free time, the faster is the reaction of the polyol with the isocyanate.

(108) The higher the difference between the value of the tack free time of the irradiated sample and the non-irradiated sample (with a tack free value of the irradiated sample, which is lower than the one of the non-irradiated one), the more photolatent is the catalyst.

(109) The catalysts and ligands which are used in the test as well as the results are collected in the following table 9.

(110) TABLE-US-00012 TABLE 9 Tack free time (stage 3/4) h 2*100 W Catalysts Ratio No irradiation 5 m/min No catalyst 13 14 Catalyst 3/ 70/30 10 8.75 Ligand 7 Catalyst 3/ 80/20 11.25 6.25 Ligand 7 Catalyst 3/ 90/10 10.75 6 Ligand 7 Catalyst 3/ 70/30 11.5 10 Ligand 3 Catalyst 3/ 80/20 12.5 7 Ligand 3 Catalyst 3/ 90/10 10.25 7 Ligand 3 Catalyst 18- 9.25 6.75 without ligand Catalyst 18/ 70/30 15.25 10 Ligand 3 Catalyst 18/ 80/20 14.5 8 Ligand 3 Catalyst 18/ 90/10 12 8.5 Ligand 3 Catalyst 18/ 70/30 14 9 Ligand 7 Catalyst 18/ 80/20 14 8.25 Ligand 7 Catalyst 18/ 90/10 12.5 8.5 Ligand 7 Catalyst 18/ 70/30 14.5 8.5 CAS 1118-71-4 Catalyst 18/ 80/20 13 8.5 CAS 1118-71-4 Catalyst 18/ 90/10 12.5 8 CAS 1118-71-4 Catalyst 24 9.5 7 without ligand Catalyst 24/ 70/30 15 8 Ligand 3 Catalyst 24/ 80/20 11.5 7.5 Ligand 3 Catalyst 24/ 90/10 11 7.75 Ligand 3 Catalyst 24/ 70/30 14 8 Ligand 7 Catalyst 24/ 80/20 11.5 7 Ligand 7 Catalyst 24/ 90/10 10 7.5 Ligand 7 Catalyst 24/CAS 70/30 13.75 8.5 1118-71-4 Catalyst 24/CAS 80/20 13 7.5 1118-71-4 Catalyst 24/CAS 90/10 11.5 8 1118-71-4

Example A10

(111) The testing samples are prepared by adding photolatent catalysts 0.025% weight of metal on solid with and without addition of sensitizer (Darocur benzophenone) to the two pack polyurethane formulation described in the example A1. The catalyst is first mixed in the component A1 and the component B1 is added just prior to the application.

(112) The mixtures are applied with a 76 m split coater on two glass plates of 30 cm length. One plate is irradiated using a UV processor from IST Metz (mercury lamps, 2*100 m) at a belt speed of 5 m/min, whereas a second one is not irradiated. The reactivity of the mixtures is determined by measuring the tack free time. Therefore the samples are set up on a drying recorder from ByK Gardner, where a needle is moving with a constant speed over the coated substrate for 24 h. The recording is carried out in the dark, at room temperature. The tack free time is the period of time needed for the sample to cure in such a manner that no tack is left on the surface upon touch of the needle in the recorder.

(113) The potlife of the formulation is visually monitored at room temperature. In fact, the time when the formulation is gelled in the flask, is determined.

(114) The lower the value of the tack free time, the faster is the reaction of the polyol with the isocyanate. The higher the difference between the value of the tack free time of the irradiated sample and the non-irradiated sample (with a tack free value of the irradiated sample, which is lower than the one of the non-irradiated one), the more photolatent is the catalyst.

(115) The higher the value of potlife, the more stable is the mixture in the flask.

(116) The catalysts which are used in the test as well as the results are collected in the following table 10.

(117) TABLE-US-00013 TABLE 10 Tack free time (stage 3/4) h Darocur Potlife 2*100 W Catalyst Benzophenone (h) No irradiation 5 m/min Catalyst 21 6 < h < 7 11.5 5.5 Catalyst 21 0.125% 6 < h < 7 12 7.25 Catalyst 22 6 < h < 7 12 6.25 Catalyst 22 0.125% 6 < h < 7 13.5 5.25 Catalyst 20 3 < h < 4 10.5 3.25 Catalyst 20 0.125% 3 < h < 4 9.5 5

Example A11

Curing of 2 Pack Polyurethane Systems

Component A2

(118) TABLE-US-00014 61 parts of a polyol (Joncryl 588; BASF SE) 0.1 parts of EFKA 3031 0.9 parts of EFKA 3033 38 parts of butylacetate

Component B2

(119) TABLE-US-00015 90 parts of aliphatic polyisocyanate [(HDI-Trimer) Basonat HI100; BASF SE] 10 parts of butylacetate

(120) The basic testing formulation of the example A11 is composed of

(121) TABLE-US-00016 32.9 parts of component A2 9.6 parts of component B2

(122) Photolatent Metal Catalytic Solution 1:

(123) The photolatent catalytic solution is composed by a mixture of catalyst 3 and ligand CAS 13988-67-5 (ratio 80/20) dissolved in 50% in butylacetate:

(124) TABLE-US-00017 40 parts of catalyst 3 10 parts of CAS 13988-67-5 50 parts of butylacetate

(125) The testing samples are prepared by adding different amounts of the photolatent metal catalytic solution to the two pack polyurethane formulation. The catalytic solution is first mixed in the component A2 and the component B2 is added just prior to the application.

(126) The mixtures are applied with 100 m draw down on three glass plates (38*7 cm). Two plates are irradiated by using a UV processor from IST Metz: One sample is exposed to Mercury lamp, 1*200 W/cm at a belt speed of 10 m/min, whereas a second sample is exposed to Gallium doped lamp, 1*200 W at a belt speed of 10 m/min.

(127) The third panel is not irradiated.

(128) The drying time of the mixture is determined by evaluating the surface cure and the through cure with to a sand test. The sand test equipment consists in funnels on wheels, which are filled by ca. 60-80 g of fine and calibrated sand grains. The funnels are moving with a constant speed over the coated substrates for 24 h. The recording is carried out at the daylight and at room temperature (23+/2 C.).

(129) The time of surface cure corresponds to the time when the sand doesn't adhere anymore to the surface of coating.

(130) The through cure is evaluated by monitoring the trace of the wheels on the coating film.

(131) The coating is cured when there are no clear spoors any more.

(132) The shorter the times of surface cure and through cure are, the faster the reaction of the polyol with the isocyanate is.

(133) The higher the difference between the curing time of the irradiated sample and the non-irradiated sample, the more photolatent is the catalytic system.

(134) The amounts of catalyst which are used in the test as well as the results are collected in the following tables 11a and 11b.

(135) TABLE-US-00018 TABLE 11a Surface cure time (h) Catalyst Mercury Gallium amount No UV lamp lamp No catalyst >19 Catalytic 0.317 g 8.5 0 0 solution 1 Catalytic 0.245 g 8.5 0 0 solution 1

(136) TABLE-US-00019 TABLE 11b Throughcure (h) Catalyst Mercury Gallium amount No UV lamp lamp No catalyst >19 Catalytic 0.317 g 11.5 2.5 3 solution1 Catalytic 0.245 g 11 5.5 3.5 solution1

Example A12

Curing of 2 Pack Polyurethane Systems

Component A3

(137) TABLE-US-00020 28.5 parts of a polyol (Joncryl 922; BASF SE) 85.6 parts of a polyol (Joncryl 507; BASF SE) 0.45 parts of EFKA 3030 1.5 parts of Baysilonoil OL, 10% ig in Butylacetate 7.65 parts of 1,2-methoxypropylacetate 26.25 parts of butylacetate

Component B3

(138) TABLE-US-00021 100 parts of aliphatic polyisocyanate [(HDI-Trimer) Basonat HI100; BASF SE]

(139) The basic testing formulation of the example A12 is composed of

(140) TABLE-US-00022 30 parts of component A3 8.73 parts of component B3

(141) Photolatent Metal Catalytic Solution 2:

(142) TABLE-US-00023 50 parts of catalyst 3 50 parts of butylacetate

(143) The photolatent catalytic solution 2 is prepared by dissolution of the catalyst in butylacetate.

(144) Photolatent Metal Catalytic Solution 3:

(145) TABLE-US-00024 40 parts of catalyst 3 10 parts of CAS 13988-67-5 50 parts of butylacetate

(146) The photolatent catalytic solution 3 is composed by a mixture of catalyst and ligand CAS 13988-67-5 (ratio 80/20) dissolved in butylacetate

(147) The testing samples are prepared by adding different amounts of the photolatent metal catalytic solution to the two pack polyurethane formulation. The catalytic solution is first mixed in the component A3 and the component B3 is added just prior to the application.

(148) The mixtures are applied with 100 m draw down on three glass plates (38*7 cm).

(149) Two plates are irradiated by using a UV processor from IST Metz: One sample is exposed to Mercury lamp, 1*200 W/cm at a belt speeds of 10 m/min, whereas a second sample is exposed to Gallium doped lamp, 1*200 W at a belt speed of 10 m/min.

(150) The third panel is not irradiated.

(151) The drying time of the mixture is determined by evaluating the surface cure and the through cure with a sand test. The sand test equipment consists in funnels on wheels, which are filled by ca. 60-80 g of fine and calibrated sand grains. The funnels are moving with a constant speed over the coated substrates for 24 h. The recording is carried out at the daylight and at room temperature (23+/2 C.).

(152) The time of surface cure corresponds to the time when the sand doesn't adhere anymore to the surface of coating. The through cure is evaluated by monitoring the trace of the wheels on the coating film. The coating is cured when there are no clear spoors any more. The shorter the times of surface cure and through cure are, the faster the reaction of the polyol with the isocyanate is.

(153) The higher the difference between the curing time of the irradiated sample and the non-irradiated sample, the more photolatent is the catalytic system.

(154) The gelled time of the formulation is determined by monitoring the capability of a spindle to move in a flask filled by the formulation. The recording is carried out at room temperature in a flask protected from light. The gelled time is the time when the spindle can not move anymore in the formulation. The longer the gelled time is, the more stable the formulation is.

(155) The amounts of catalyst which are used in the test as well as the results are collected in the following tables 12a and 12b.

(156) TABLE-US-00025 TABLE 12a Surface cure time (h) Catalyst Gelled Mercury Gallium Catalyst amount time No UV lamp lamp No catalyst 14 h 55 13 Catalytic 1.62 g <15 min <0.5 0 0 solution 2 Catalytic 0.81 g 04 h 25 8 0 0 solution 3

(157) TABLE-US-00026 TABLE 12b Through cure time(h) Catalyst Gelled Mercury Gallium Catalyst amount time No UV lamp lamp No catalyst 14 h 55 24 Catalytic 1.62 g <15 min 3 0 0 solution 2 Catalytic 0.81 g 04 h 25 8.5 3.5 3.5 solution 3

Example A13

(158) Influence of light stabilizers and light absorbers on the curing of 2 pack polyurethane systems:

Component A4

(159) TABLE-US-00027 28.1 parts of a polyol (Joncryl 922; BASF SE) 84.4 parts of a polyol (Joncryl 507; BASF SE) 0.45 parts of EFKA 3030 1.5 parts of Baysilonoil OL, 10% ig in nutylacetate 1.05 parts of Tinuvin 292 (HALS- light stabilizer) provided by BASF SE 1.11 parts of Tinuvin 384-2 (UV absorber) provided by BASF SE 7.65 parts of 1,2-methoxypropylacetate 25.89 parts of butylacetate

Component B4

(160) TABLE-US-00028 100 parts of aliphatic polyisocyanate [(HDI-Trimer) Basonat HI100; BASF SE]

(161) The basic testing formulation of the example A13 is composed of

(162) TABLE-US-00029 30 parts of component A4 8.73 parts of component B4

(163) Photolatent Metal Catalytic Solution 3:

(164) TABLE-US-00030 40 parts of catalyst 3 10 parts of CAS 13988-67-5 50 parts of butylacetate

(165) The photolatent catalytic solution 3 is composed by a mixture of catalyst and ligands CAS 13988-67-5 (ration 80/20) dissolved in butylacetate.

(166) The testing samples are prepared by adding different amounts of the photolatent metal catalytic solution to the two pack polyurethane formulation. The catalytic solution is first mixed in the component A4 and the component B4 is added just prior to the application.

(167) The mixtures are applied with 100 m draw down on three glass plates (38*7 cm).

(168) Two plates are irradiated by using a UV processor from IST Metz: One sample is exposed to Mercury lamp, 1*200 W/cm at a belt speeds of 10 m/min, whereas a second sample is exposed to Gallium doped lamp, 1*200 W at a belt speed of 10 m/min.

(169) The third panel is not irradiated.

(170) The drying time of the mixture is determined by evaluating the surface cure and the through cure with a sand test. The sand test equipment consists in funnels on wheels, which are filled by ca. 60-80 g of fine and calibrated sand grains. The funnels are moving with a constant speed over the coated substrates for 24 h. The recording is carried out at the daylight and at room temperature (23+/2 C.).

(171) The time of surface cure corresponds to the time when the sand doesn't adhere anymore to the surface of coating. The through cure is evaluated by monitoring the trace of the wheels on the coating film. The coating is cured when there are no clear spoors any more. The shorter the times of surface cure and through cure are, the faster the reaction of the polyol with the isocyanate is. The higher the difference between the curing time of the irradiated sample and the non-irradiated sample, the more photolatent is the catalytic system.

(172) The gelled time of the formulation is determined by monitoring the capability of a spindle to move in a flask filled by the formulation. The recorded is carried out at room temperature in a flask protected from light. The gelled time is the time when the spindle can not move anymore in the formulation. The longer the gelled time is, the more stable the formulation is.

(173) The amounts of catalyst which are used in the test as well as the results are collected in the following tables 13a and 13b.

(174) TABLE-US-00031 TABLE 13a Surface cure time (h) Catalyst Gelled Mercury Gallium Catalyst amount time No UV lamp lamp No catalyst 13 h 48 16 Catalytic 0.40 g 04 h 22 8.5 3 2 solution 3 Catalytic 0.80 g 04 h 49 9 3 2.5 solution 3

(175) TABLE-US-00032 TABLE 13b Through cure (h) Catalyst Gelled Mercury Gallium Catalyst amount time No UV lamp lamp No catalyst 13 h 48 15.5 Catalytic 0.40 g 4 h 22 9 3.5 7 solution 3 Catalytic 0.80 g 04 h 25 10 7 4 solution 3