PHOTO-LATENT TITANIUM OXO-CHELATE CATALYSTS

Abstract

A titanium-oxo-chelate catalyst formulation, comprising: (i) at least one compound of the formula (I), wherein R.sub.1, 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 and R.sub.12 independently of each other are for example hydrogen, halogen, C.sub.1-C.sub.20alkyl, C.sub.6-C.sub.14aryl which is unsubstituted or substituted; or R.sub.1, R.sub.2 and R.sub.3 and/or R.sub.4, R.sub.5 and R.sub.6 and/or R.sub.7, R.sub.8 and R.sub.9 and/or R.sub.10, R.sub.11 and R.sub.12 together with the C-atom to which they are attached each form a C.sub.6-C.sub.14aryl group which is unsubstituted or substituted; or R.sub.1 and R.sub.2 and/or R.sub.4 and R.sub.5 and/or R.sub.7 and R.sub.8 and/or R.sub.10 and R.sub.11 together with the C-atom to which they are attached form a 5- to 7-membered carbocyclic ring; at least one chelate ligand compound of the formula (IIa), (IIb) or (IIc), wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are defined as above for formula (I), is suitable as a photolatent catalyst formulation for polymerizing compounds, which are capable to crosslink in the presence of a Lewis acid.

##STR00001##

Claims

1-16. (canceled)

17. A titanium-oxo-chelate catalyst compound of the formula (IA) or (IB) ##STR00043## wherein R.sub.20, R.sub.20, R.sub.20, R.sub.21, R.sub.21 and R.sub.21 independently of each other are hydrogen, halogen, C.sub.1-C.sub.20alkyl, which is unsubstituted or substituted by one or more OR.sub.13 or COOR.sub.13, or are C.sub.6-C.sub.14aryl which is unsubstituted or is substituted by one or more C.sub.1-C.sub.8alkyl, halogen, OR.sub.13 or NR.sub.13R.sub.14; provided that only one of R.sub.20, R.sub.20 and R.sub.20 in the group ##STR00044## and only one of R.sub.21, R.sub.21 and R.sub.21 in the group ##STR00045## can be hydrogen; or R.sub.20 and R.sub.20 and/or R.sub.21 and R.sub.21 together with the C-atom to which they are attached form a 5- to 7-membered carbocyclic ring, R.sub.22, R.sub.23, R.sub.24 independently of each other are hydrogen, halogen, C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkoxy, C.sub.6-C.sub.14aryl, C.sub.1-C.sub.8alkanoyl, C.sub.1-C.sub.8alkanoyloxy, C.sub.7-C.sub.15aroyl, C.sub.7-C.sub.15aroyloxy, nitrile, nitro, C.sub.1-C.sub.8alkylthio, C.sub.6-C.sub.14arylthio or NR.sub.37R.sub.38; R.sub.25, R.sub.26, R.sub.27, R.sub.28, R.sub.29, R.sub.30, R.sub.31, R.sub.32, R.sub.33, R.sub.34, R.sub.35 and R.sub.36 independently of each other are hydrogen, C.sub.1-C.sub.8alkyl which is unsubstituted or substituted by one or more OR.sub.13 or COOR.sub.14, or are C.sub.6-C.sub.14aryl which is unsubstituted or is substituted by one or more C.sub.1-C.sub.8alkyl, OR.sub.13 or NR.sub.13R.sub.14; or two radicals R.sub.25 and R.sub.26 and/or two radicals R.sub.28 and R.sub.29 and/or two radicals R.sub.31 and R.sub.32 and/or two radicals R.sub.34 and R.sub.35 together with the C-atom to which they are attached form a 5- to 7-membered carbocyclic ring; provided that only one of R.sub.25, R.sub.26, R.sub.27 in the group ##STR00046## and only one of R.sub.28, R.sub.29, R.sub.30 in the group ##STR00047## and only one of R.sub.31, R.sub.32, R.sub.33 in the group ##STR00048## and only one of R.sub.34, R.sub.35, R.sub.36 in the group ##STR00049## can be hydrogen; and provided that R.sub.25, R.sub.26, R.sub.27, R.sub.28, R.sub.29, R.sub.30, R.sub.31, R.sub.32, R.sub.33, R.sub.34, R.sub.35 and R.sub.36 are not simultaneously methyl; R.sub.13 and R.sub.14 independently of each other are C.sub.1-C.sub.8alkyl; R.sub.37 and R.sub.38 independently of each other are hydrogen, C.sub.1-C.sub.8alkyl or C.sub.6-C.sub.14aryl, or R.sub.37 and R.sub.38 together with the N-atom to which they are attached form a 5- or 6-form a 5- or 6-membered saturated or unsaturated ring, which ring optionally in addition to the N-atom comprises a further N-atom or O-atom.

18. The titanium-oxo-chelate catalyst compound of claim 17, wherein two radicals R.sub.25 and R.sub.26 and/or two radicals R.sub.28 and R.sub.29 and/or two radicals R.sub.31 and R.sub.32 and/or two radicals R.sub.34 and R.sub.35 together with the C-atom to which they are attached form a 5- to 7-membered carbocyclic ring.

19. The titanium-oxo-chelate catalyst compound of claim 18, wherein the 5- to 7-membered carbocyclic ring(s) is/are selected from ##STR00050## wherein R.sub.x2 is R.sub.27, R.sub.36, R.sub.30 and/or R.sub.33, R.sub.y2 is C.sub.1-C.sub.20alkyl, n is an integer 1-5 and m is an integer 1-4.

20. The titanium-oxo-chelate catalyst compound of claim 17, wherein in formula (IA) R.sub.20, R.sub.20, R.sub.20 independently of each other are hydrogen, halogen or C.sub.1-C.sub.20 alkyl, which is unsubstituted or substituted by one or more OR.sub.13 or COOR.sub.13; R.sub.21, R.sub.21, R.sub.21 independently of each other are hydrogen, halogen or C.sub.1-C.sub.20 alkyl, which is unsubstituted or substituted by one or more OR.sub.13 or COOR.sub.13; R.sub.22, R.sub.23, R.sub.24 independently of each other are hydrogen, C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8 alkoxy, C.sub.1-C.sub.8 alkanoyl, C.sub.1-C.sub.8 alkanoyloxy, chloro, nitrile, nitro, C.sub.1-C.sub.8 alkylthio, C.sub.6-C.sub.14 arylthio or NR.sub.37R.sub.38; and in formula (IB) R.sub.25, R.sub.26, R.sub.27 independently of each other are hydrogen, C.sub.1-C.sub.8 alkyl which is unsubstituted or substituted by one or more OR.sub.13 or COOR.sub.14, or two radicals R.sub.25 and R.sub.26 together with the C-atom to which they are attached form a cyclopentyl or cyclohexyl ring; R.sub.31, R.sub.32, R.sub.33 independently of each other are hydrogen, C.sub.1-C.sub.8 alkyl which is unsubstituted or substituted by one or more OR.sub.13 or COOR.sub.14, or two radicals R.sub.31 and R.sub.32 together with the C-atom to which they are attached form a cyclopentyl or cyclohexyl ring; R.sub.28, R.sub.29, R.sub.30 independently of each other are hydrogen, C.sub.1-C.sub.8 alkyl which is unsubstituted or substituted by one or more OR.sub.13 or COOR.sub.14, or two radicals R.sub.28 and R.sub.29 together with the C-atom to which they are attached form a cyclopentyl or cyclohexyl ring; R.sub.34, R.sub.35, R.sub.36 independently of each other are hydrogen, C.sub.1-C.sub.8alkyl which is unsubstituted or substituted by one or more OR.sub.13 or COOR.sub.14, or two radicals R.sub.34 and R.sub.35 together with the C-atom to which they are attached form a cyclopentyl or cyclohexyl ring.

21. The titanium-oxo-chelate catalyst compound of claim 20, wherein in formula (IA) R.sub.20, R.sub.20, R.sub.20 independently of each other are hydrogen, halogen or C.sub.1-C.sub.8 alkyl; R.sub.21, R.sub.21, R.sub.21 independently of each other are hydrogen, halogen or C.sub.1-C.sub.8 alkyl; R.sub.22, R.sub.23, R.sub.24 independently of each other are hydrogen, C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8 alkoxy, C.sub.1-C.sub.8 alkanoyl, C.sub.1-C.sub.8 alkanoyloxy or NR.sub.37R.sub.38; and in formula (IB) R.sub.25, R.sub.26, R.sub.27 independently of each other are hydrogen, C.sub.1-C.sub.8 alkyl, or two radicals R.sub.25 and R.sub.26 together with the C-atom to which they are attached form a cyclopentyl or cyclohexyl ring; R.sub.31, R.sub.32, R.sub.33 independently of each other are hydrogen, C.sub.1-C.sub.8 alkyl, or two radicals R.sub.31 and R.sub.32 together with the C-atom to which they are attached form a cyclopentyl or cyclohexyl ring; R.sub.28, R.sub.29, R.sub.30 independently of each other are hydrogen, C.sub.1-C.sub.8 alkyl, or two radicals R.sub.28 and R.sub.29 together with the C-atom to which they are attached form a cyclopentyl or cyclohexyl ring; R.sub.34, R.sub.35, R.sub.36 independently of each other are hydrogen, C.sub.1-C.sub.8alkyl, or two radicals R.sub.34 and R.sub.35 together with the C-atom to which they are attached form a cyclopentyl or cyclohexyl ring;

22. The titanium-oxo-chelate catalyst compound of claim 21, wherein in formula (IA) R.sub.20, R.sub.20, R.sub.20 independently of each other are hydrogen, fluoro or C.sub.1-C.sub.8 alkyl; R.sub.21, R.sub.21, R.sub.21 independently of each other are hydrogen, fluoro or C.sub.1-C.sub.8 alkyl, R.sub.22, R.sub.23, R.sub.24 independently of each other are hydrogen, C.sub.1-C.sub.8 alkyl, C.sub.1-C.sub.8 alkoxy, or NR.sub.37R.sub.38; and in formula (IB) R.sub.25, R.sub.26, R.sub.27 independently of each other are hydrogen, C.sub.1-C.sub.8 alkyl which is unsubstituted or substituted by one or more OR.sub.13 or COOR.sub.14; R.sub.31, R.sub.32, R.sub.33 independently of each other are hydrogen, C.sub.1-C.sub.8 alkyl which is unsubstituted or substituted by one or more OR.sub.13 or COOR.sub.14; R.sub.28, R.sub.29, R.sub.30 independently of each other are hydrogen, C.sub.1-C.sub.8 alkyl which is unsubstituted or substituted by one or more OR.sub.13 or COOR.sub.14; R.sub.34, R.sub.35, R.sub.36 independently of each other are hydrogen, C.sub.1-C.sub.8 alkyl which is unsubstituted or substituted by one or more OR.sub.13 or COOR.sub.14.

23. The titanium-oxo-chelate catalyst compound of claim 22, wherein in formula (IA) R.sub.20, R.sub.20, R.sub.20 are hydrogen, fluoro or methyl. R.sub.21, R.sub.21, R.sub.21 are hydrogen, fluoro or methyl. R.sub.22, R.sub.23, R.sub.24 independently of each other are hydrogen, methyl, methoxy or dimethylamino and in formula (IB) R.sub.25, R.sub.26, R.sub.27 independently of each other are hydrogen or C.sub.1-C.sub.8 alkyl; R.sub.31, R.sub.32, R.sub.33 independently of each other are hydrogen or C.sub.1-C.sub.8 alkyl; R.sub.28, R.sub.29, R.sub.30 independently of each other are hydrogen or C.sub.1-C.sub.8 alkyl; R.sub.34, R.sub.35, R.sub.36 independently of each other are hydrogen or C.sub.1-C.sub.8 alkyl.

24. The titanium-oxo-chelate catalyst compound of claim 23, wherein in formula (IA) the groups R.sub.20, R.sub.20R.sub.20C and R.sub.21R.sub.21R.sub.21C are identical; and in formula (IB) the groups R.sub.25R.sub.26R.sub.27C and R.sub.31R.sub.32R.sub.33C are identical and/or the groups R.sub.28R.sub.29R.sub.30C and R.sub.34R.sub.35R.sub.36C are identical.

25. A polymerizable composition comprising: (a) at least one component which is capable of a polyaddition or polycondensation reaction in the presence of a Lewis-acid type reactant; and (b) a Titanium-oxo-chelate catalyst compound of claim 17.

26. A polymerizable composition of claim 25 comprising as component (a) (a1) at least one blocked or unblocked isocyanate or isothiocyanate component, and (a2) at least one polyol.

27. A polymerizable composition of claim 25, which comprises 0.001 to 15% by weight, preferably 0.01 to 5% by weight, of the titanium-oxo-chelate catalyst compound, based on the total composition.

28. A coated substrate coated on at least one surface with the composition of claim 25.

29. A polymerized or crosslinked composition of claim 25.

30. A process for polymerizing compounds, which are capable to crosslink in the presence of a Lewis acid, characterized in that a titanium-oxo-chelate catalyst compound as defined in claim 17 is added to the compounds which are capable to crosslink in the presence of a Lewis acid and the resulting mixture is irradiated with electromagnetic radiation of a wavelength range of 200-800 nm.

31. A process of claim 30, characterized in that instead of irradiating with electromagnetic radiation the mixture is subjected to a heat treatment, or the mixture is irradiated with electromagnetic radiation and simultaneously with or after the irradiation subjected to a heat treatment.

32. A process of claim 30 for the preparation of adhesives, sealings, coatings, potting components, printing inks, printing plates, foams, moulding compounds, or photostructured layers.

33. The titanium-oxo-chelate catalyst compound of claim 17 being a compound of the formula IB ##STR00051## wherein R.sub.25, R.sub.26, R.sub.27 and R.sub.28 independently of each other are hydrogen, C.sub.1-C.sub.8alkyl which is unsubstituted or substituted by one or more OR.sub.13 or COOR.sub.14, or are C.sub.6-C.sub.14aryl which is unsubstituted or is substituted by one or more C.sub.1-C.sub.8alkyl, OR.sub.13 or NR.sub.13R.sub.14; or two radicals R.sub.25 and R.sub.26 together with the C-atom to which they are attached and/or or two radicals R.sub.27 and R.sub.28 together with the C-atom to which they are attached form a 5- to 7-membered carbocyclic ring.

Description

APPLICATION EXAMPLES

[0201] The following commercially available 1, 3-diketones are used in the application examples:

##STR00042##

[0202] Curing and Pot-Life of a Two Packs Polyurethane System Based on a Polyacrylic Polyol and an Aliphatic Polyisocyanate:

[0203] 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.

[0204] In the following examples A1 to A4, 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 A

[0205]

TABLE-US-00002 73.1 parts of a polyacrylate polyol (70% in butyl acetate; Desmophen A HS 1 170 BA, provided by Bayer Material Science) 2.3 parts of an additive blend (consisting of 0.9 parts of a solution of polyacrylates as flow improvers, 0.7 parts of a silicon defoamer and 0.7 parts of a polyether modified dimethylpolysiloxane as silicon surface additive) 24.6 parts of xylene/methoxypropylacetate/butylacetate (1/1/1)

Component B

[0206] Aliphatic polyisocyanate [(Hexamethylenediisocyanate-Trimer) 90% in solvent blend; Desmodur N 3390, provided by Bayer Material Science]

[0207] The basic testing formulations are composed of:

TABLE-US-00003 7.52 parts of component A 2.00 parts of component B

Example A1: Catalyst Efficiency Before and after Activation by UV Light

[0208] The testing samples are prepared by adding the photolatent Ti catalysts (Catalyst) to 7.52 g of component A of the basic testing formulation as described above.

[0209] After completing the mixing of component A with 2 g of component B, the mixtures are applied with a 76.Math. split coater on two glass plates of 30 cm length. One plate is irradiated using an UV processor from 1ST Metz (2 mercury lamps operated at 100 W/cm) at a belt speed of 5 m/min, whereas the second glass plate is not irradiated. The reactivity of the mixtures is determined by measuring the tack free time of the applied formulation (coated glass plate) by means of a drying recorder from Byk Gardner, where a nee-die is moving with a constant speed over the coated substrate for 24 hrs. 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 from the recorder.

[0210] The lower the value of the tack free time, the faster is the addition reaction of the polyol to the polyisocyanate.

[0211] 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. The catalysts which are used in the test as well as the results are collected in the following table 1.

TABLE-US-00004 TABLE 1 Tack free time (stage 3/4) in hrs. Catalyst/(g) No UV irradiation 2 100 W/cm @ 5 m/min Catalyst 1/(0.0174) 13 7 Catalyst 2/(0.0185) 11 6.75 Catalyst 3/(0.0174) 10 6.25 Catalyst 4/(0.0185) 9.25 4.75 Catalyst 7/(0.0166) 9 5.5 Catalyst 8/(0.0139) 11 6 Catalyst 9/(0.0155) 10.5 7

Example A2: Formulation Stability (Pot-Life)

[0212] The testing samples are prepared by adding the Ti catalyst (Catalyst) and 1,3-diketone free ligand (Additive) to 7.52 g of component A of the basic testing formulation of example A1. After mixing component A with 2.0 g of component B, the visual pot-life of the formulation (time where no change in viscosity is visible) is observed: the gelled time, the time to considerable viscosity, and the time to high viscosity are determined, while storing the samples in dark flasks.

[0213] The catalysts and additives which are used in the test as well as the results of the tests are collected in the following table 2.

TABLE-US-00005 TABLE 2 Gelled Considerably Highly Time viscous viscous Catalyst/(g) Additive/(g) (min.) (min.) (min.) >600 >3000 Catalyst 13/ 65 115 140 (0.059) Catalyst 13/ CAS 13988- 65 165 200 (0.059) 67-5/(0.007) Catalyst 13/ CAS 13988- 180 285 305 (0.059 67-5/(0.015) Catalyst 13/ CAS 13988- 510 < t < 510 < t < 510 < t < (0.059) 67-5/(0.059) 960 960 960 Catalyst 13/ CAS 326-06- 270 390 460 (0.059) 7/(0.015) Catalyst 13/ CAS 120-46- 120 210 280 (0.059) 7/0.015 Catalyst 13/ CAS 18362- 210 330 390 (0.059) 64-6/(0.015) Catalyst 13/ CAS 1522-22- 120 240 280 (0.059) 1/(0.015) Catalyst 13/ CAS 22767- 240 390 510 (0.059) 90-4/(0.015) Catalyst 13/ CAS 1118- 180 300 390 (0.059) 71-4/(0.015) Catalyst 8/ 120 210 255 (0.055) Catalyst 8/ CAS 13988- 180 300 390 (0.055) 67-5/(0.014) Catalyst 12/ 300 510 540 < t < (0.054) 990 Catalyst 12/ CAS 1118- 540 < t < 540 < t < 540 < t < (0.054) 71-4/(0.013) 990 990 990 Catalyst 12/ CAS 13988- 540 < t < 540 < t < 540 < t < (0.054) 67-5/(0.013) 990 990 990

Example A 3: Formulation StabilityShelf-Life (Viscosity Evolution)

[0214] The testing samples are prepared by adding photolatent Ti catalyst (Catalyst), and 1, 3-diketone free ligand (CAS 13988-67-5) to 7.52 g of component A 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.

[0215] After admixing component A with 2 g of component B, the mixtures are stored in the dark at room temperature. The shelflife 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 the formulation and each hour for 7 h. The viscosity increases with the time. The lower the increase of the viscosity, the longer is the shelflife of the formulation and consequently the larger is the working window. The catalyst and ligand which are used in the experiment as well as results are presented in the following table 3.

TABLE-US-00006 TABLE 3 Catalyst (g)/ Viscosity at 25 C. (poises) Ligand CAS (g) Ratio 0 h 1 h 2 h 3 h 4 h 5 h 6 h 7 h Catalyst 2 (0.0185) 1.4 2.7 4.3 7.8 16.6 35.2 ## ## Catalyst 2 (0.0185)/ 80/20 1.2 1.5 1.9 2.4 3.1 3.6 5 58 13988-67-5 (0.0046) Catalyst 2 (0.0185)/ 70/30 1.2 1.5 1.8 2 2.5 2.9 3.5 4 13988-67-5 (0.0079) Catalyst 3 (0.0174) 1.6 3.5 7.4 16 52 ## ## ## Catalyst 3 (0.0174)/ 80/20 1.1 2 3 4.2 6 9 12.8 17.6 13988-67-5 (0.0044) Catalyst 3 (0.0174)/ 70/30 1.1 1.8 3 3.8 5 7 10 12.4 13988-67-5 (0.0075) Catalyst 4 (0.0185) 1.8 3.8 6.5 28 ## ## ## ## Catalyst 4 (0.0185)/ 80/20 1.1 2.1 2.8 4 6.1 9.3 12 16 13988-67-5 (0.0046) Catalyst 4 (0.0185)/ 70/30 1.1 1.7 2.5 3.5 4.2 5.8 7.1 8.8 13988-67-5 (0.0079) Catalyst 7 (0.0166) 1.6 3.3 6 13 34.4 ## ## ## Catalyst 7 (0.0166)/ 80/20 1.1 1.7 2.4 3.5 4.2 5.8 8 10.8 13988-67-5 (0.0042) Catalyst 7 (0.0166)/ 70/30 1.2 1.5 2.1 2.8 3.6 5.6 7 7.8 13988-67-5 (0.0071) ## Gelled

Example A 4: Ratio Catalyst/Ligand Efficiency Before and after Activation by UV-Light

[0216] The testing samples are prepared by adding photolatent Ti catalysts and 1,3-diketone free ligand (CAS 13988-67-5) to 7.52 g of component A 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.

[0217] After mixing component A with 2 g of component B, 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 1ST Metz (2 mercury lamps operated at 100 W/cm) at a belt speed of 5 m/min, whereas the 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 for 24 h over the coated substrate. 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.

[0218] The lower the value of the tack free time, the faster is the reaction of the polyol with the isocyanate.

[0219] 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. The catalysts and ligand which are used in the test as well as the results are collected in the following table 4.

TABLE-US-00007 TABLE 4 Catalyst (g) Tack free time (stage 3/4) h ligand (g) Ratio No irradiation 2 100 W 5 m/min Catalyst 2 (0.0185)/ 80/20 16 13 CAS 13988-67-5 (0.0046) Catalyst 2 (0.0185)/ 70/30 17 11.5 CAS 13988-67-5 (0.0079) Catalyst 3 (0.0174)/ 80/20 14.5 11 CAS 13988-67-5 (0.0044) Catalyst 3 (0.0174)/ 70/30 13.5 9.5 CAS 13988-67-5 (0.0075) Catalyst 4 (0.0185)/ 80/20 14 8 CAS 13988-67-5 (0.0046) Catalyst 4 (0.0185)/ 70/30 14.5 6.5 CAS 13988-67-5 (0.0079) Catalyst7 (0.0166)/ 80/20 12.5 9.75 CAS 13988-67-5 (0.0042) Catalyst7 (0.0166)/ 70/30 14.5 9.75 CAS 13988-67-5 (0.0071)

[0220] In the following Example A5 Component A includes all ingredients other than the polyisocyanate. The photolatent catalyst (Catalyst 12) alone or in combination with 1,3 diketone (CAS11 18-71-4) is added into Component A prior to the addition of Component B.

Component A

[0221]

TABLE-US-00008 104 parts of a polyacrylate polyol (80% in butylacetate; Joncryl507, provided by BASF SE) 1.2 parts of an organically modified polysiloxane, EFKA 3030, used as levelling agent 51.2 parts of Butylacetate (BuAc)

Component B

[0222] Aliphatic polyisocyanate [(Hexamethylenediisocyanate-Trimer), 100% solid; Basonat HI 100, provided by BASF SE]

[0223] The basic testing formulations are composed of:

TABLE-US-00009 40 parts of component A 10.24 parts of component B

[0224] Prior to their addition in the Component A, the following catalytic solutions containing the catalyst and the ligand are prepared:

TABLE-US-00010 Catalyst 12/CAS Catalyst 12 1118-71-4 (70/30) (10% in BuAc) (50% in BuAc) Catalyst 12 10 35 CAS 1118-71-4 15 butylacetate (BuAc) 90 50 % metal 1.10% 3.90%

Example A5: Reactivity after UV-Exposure of Catalyst 12 with and without Addition of Ligand CAS 1 118-71-4

[0225] The testing samples are prepared by adding the catalytic solutions, described above to component A of the basic testing formulation.

[0226] After completing the mixing of component A with 10.24 of component B, the mixtures are applied with a 76 m split coater on three glass plates of 30 cm length. One plate is three times in a row, irradiated using an UV processor from 1ST Metz, type BLK-U-30-21-SS-tr-N2 (1 mercury lamp operated at 100 W/cm) at a belt speed of 10 m/min, the second plate is irradiated during 6 minutes under Dr. Hoenle Lamp-Type UVA spot 400T (distance is 20 cm), whereas the third glass plate is not irradiated. The reactivity of the mixtures is determined by measuring the tack free time of the applied formulation (coated glass plate) by means of a drying recorder from Byk Gardner, where a needle is moving with a constant speed over the coated substrate for 24 hrs. 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 from the recorder.

[0227] The lower the value of the tack free time, the faster is the addition reaction of the polyol to the polyisocyanate.

[0228] 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. The catalysts which are used in the test as well as the results are collected in the following table 5.

TABLE-US-00011 TABLE 5 Tack free time (stage 3/4) in hrs. No UV 3 passes under 6 min under Catalyst (g) irradiation 1 100 W/cm @ 10 m/min UVA spot Catalyst 12 21 14.5 4.75 (10% in BuAc) 0.716 g Catalyst 12 18.5 16 6.75 (10% in BuAc) 0.358 g Catalyst 12/CAS 16.25 9 3.25 1118-71-4 (70/30) (50% in BuAc) 0.2 g

Example A6: Adhesive Formulation for Film to Film Lamination

[0229] The solventless reactive polyurethane test adhesive is a common system for film to film lamination in the flexible packaging industry. Prior to the application 14 parts of the isocyanate component of the solventless adhesive are dissolved in 7 parts ethylacetate and then 4 parts of the hydroxy component are added and mixed. The photolatent catalyst 12 is mixed into the hydroxy component.

[0230] The adhesive is knife-coated in a dry layer thickness of 2.5 g/m.sup.2 (solids) onto various commercially available polymer films. After being coated the samples are dried with a stream of hot air and then treated with UV light by a standard mercury medium pressure vapour lamp. The coated polymer films are laminated to a second polymer film in a calander at 23 C. and under a pressure of 6.5 bar. The prepared film-to-film laminates are well adhering.