VISIBLE LIGHT-CURING OF PHOTOCURABLE COMPOSITIONS IN AMBIENT ATMOSPHERE

Abstract

A photocurable composition is curable by exposure to visible light, and comprises a free-radical polymerizable compound and a photoinitiating system, the photoinitiating system comprising a) a dye which is excitable by visible light and has a triplet energy form 150 kJ/mol to 250 kJ/mol, such as Eosin Yellow and Fluorescein, and b) an -halogen carbonyl compound. Preferably, the composition comprises a compound with a CH-acidic hydrogen atom adjacent to at least one carbonyl group. The composition is cured by visible light in an oxygen-containing atmosphere and results in tack-free, colorless coatings.

Claims

1: A photocurable composition, comprising: a free-radical polymerizable compound, and a photoinitiating system, the photoinitiating system comprising: a) a dye which is excitable by visible light and has a triplet energy form 150 kJ/mol to 250 kJ/mol, and b) an -halogen carbonyl compound, wherein the photocurable composition is curable by exposure to visible light.

2: The photocurable composition according to claim 1, in which dye a) comprises a xanthen dye.

3: The photocurable composition according to claim 2, in which dye a) is at least one member selected from the group consisting of Eosin Yellow and Fluorescein.

4: The photocurable composition according to claim 1, in which the -halogen carbonyl compound b) is a compound represented by formula IIa or IIb: ##STR00004## wherein: R.sup.2 represents a halogen atom, R.sup.3 represents a halogen atom or a hydrogen atom, R.sup.4, R.sup.5 independently represent aryl, C.sub.1-C.sub.20-alkoxy, C.sub.1-C.sub.20-alkyl, or R.sup.4 and R.sup.5 together with the carbon atom to which they are attached and the intervening carbon atoms form a 5 to 7 membered cyclic structure which may have 1 or 2 heteroatoms and/or a carbonyl group, wherein the 5 to 7 membered cyclic structure can be substituted by one to three substituents selected from C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy or aryl substituents, and/or may be annelated by a saturated or unsaturated cycle, and R.sup.6 represents (4-halogen)-phenyl or (2-halogen)-acyl.

5: The photocurable composition according to claim 4, in which the -halogen carbonyl compound b) is at least one member selected from the group consisting of 5,5-dibromomeldrum's acid; 2-bromo-1,3-indandione; diethylbromomalonate; 2-bromo-1,3-diphenyl-prop-ane-1,3-dione; 2,2,4-tribromoacetophenon; and 1,4-dibromo-2,3-butandione.

6: The photocurable composition according to claim 1, in which the free-radical polymerizable compound is an ,-ethylenically unsaturated compound.

7: The photocurable composition according to claim 6, in which the free-radical polymerizable compound comprises a polyethylenically unsaturated compound.

8: The photocurable composition according to claim 6, in which the free-radical polymerizable compound is at least one member selected from the group consisting of a C.sub.1-C.sub.20-alkyl(meth)acrylate; a C.sub.1-C.sub.20-hydroxyalkyl(meth)acrylate; a polyol poly(meth)acrylate; a heterocycloalkylalkyl(meth)acrylate; a cycloalkyl(methyl)acrylate; a cycloalkylalkyl(meth)acrylate; and an amine modified polyetheracrylate.

9: The photocurable composition according to claim 8, in which the free-radical polymerizable compound is at least one member selected from the group consisting of 2-hydroxyethyl methacrylate; dipentaerytrithol pentaacrylate; tetrahydrofurfuryl acrylate; tetrahydrofurfuryl methacrylate; trimethylolpropane triacrylate; trimethylolpropane trimethylacrylate; poly(propyleneglycole) dimethacrylate; trimethylolpropaneformal monoacrylate; Laromer 9054; pentaerythritol tetraacrylate; and diethylenglycole dimethacrylate.

10: The photocurable composition according to claim 1, which additionally comprises a compound with a CH-acidic hydrogen atom adjacent to at least one carbonyl group.

11: The photocurable composition according to claim 10, in which the compound with a CH-acidic hydrogen atom adjacent to at least one carbonyl group is at least one member selected from the group consisting of methyl meldrum's acid; 1,3-dimethylbarbituric acid; and 2,2-dimethyl-1,3-dioxane-4,6-dione.

12: The photocurable composition according to claim 1, which further comprises a filler.

13: The photocurable composition according to claim 12, in which the filler is at least one member selected from the group consisting of barium sulfate; titanium oxide; a silicone; a polymers; and a copolymer.

14: A method for coating a substrate, the method comprising: a) applying to the substrate a photocurable composition according to claim 1, and b) curing exposing the photocurable composition with visible light.

15: A method for sealing together two substrates, the method comprising: a) applying a photocurable composition according to claim 1 to at least one of the two substrates. b) mating the substrates together to form an assembly, and c) curing the photocurable composition within the assembly with visible light, wherein one of the two substrates is transparent.

16: The method according to claim 14, wherein the curing is carried out in an atmosphere that comprises oxygen.

17: The method according to claim 15, wherein the curing is carried out in an atmosphere that comprises oxygen.

18: The photocurable composition according to claim 4, wherein R.sup.2 represents Cl, Br, or I.

Description

EXAMPLE 1

[0065] According to the general procedure above, 5 mL 2-hydroxyethyl methacrylate, 25 mg 2-bromo-1,3-diphenyl-propane-1,3-dione, 25 mg 1,3-dimethylbarbituric acid and 250 L Eosin Yellow disodium salt (0.05 M in MeOH) were mixed and irradiated for 10-30 minutes via an green light emitting LED. Afterwards, the coating was yellow, transparent and tack-free.

EXAMPLE 2

[0066] According to the general procedure above, 1 mL amine modified polyether acrylate (CN UVA 421), 20 L diethylbromo malonate and 50 L Fluorescein disodium salt (0.05 M in MeOH) were mixed and irradiated for 10-30 minutes via a blue light emitting LED. Afterwards, the coating was slightly yellow, transparent and tack-free.

EXAMPLE 3

[0067] According to the general procedure above, 5 mL tetrahydrofurfuryl methacrylate, 20 mg 5,5-dibromomeldrum's acid, and 50 L Eosin Yellow disodium salt (0.05 M in MeOH) were mixed and irradiated for 10-30 minutes via an green light emitting LED. Afterwards, the coating was yellow, transparent and tack-free.

EXAMPLE 4

[0068] According to the general procedure above, 5 mL 2-hydroxyethyl methacrylate methacrylate, 10 mg 2-bromo-1,3-indandione, and 250 L Fluorescein disodium salt (0.05 M in MeOH) were mixed and irradiated for 10-30 minutes via a blue light emitting LED. Afterwards, the coating was light yellow, transparent and tack-free.

EXAMPLE 5

[0069] According to the general procedure above, 5 mL 2-hydroxyethyl methacrylate, 20 mg 5,5-dibromomeldrum's acid, and 50 L Eosin Yellow disodium salt (0.05 M in MeOH) were mixed and irradiated for 10-30 minutes via an green light emitting LED. Afterwards, the coating was yellow, transparent and tack-free.

EXAMPLE 6

[0070] According to the general procedure above, 5 mL 2-hydroxyethyl methacrylate, 125 L 1,4-dibromo-2,3-butandione, 260 mg 1,3-dimethylbarbituric acid and 250 L Fluorescein disodium salt (0.05 M in MeOH) were mixed and irradiated for 10-30 minutes via a blue light emitting LED. Afterwards, the coating was light yellow, transparent and tack-free.

EXAMPLE 7

[0071] According to the general procedure above, 5 mL pentaerythritol pentaacrylate, 20 mg 5,5-dibromomeldrum's acid, and 50 L Eosin Yellow disodium salt (0.05 M in MeOH) were mixed and irradiated for 10-30 minutes via an green light emitting LED. Afterwards, the coating was yellow, transparent tack-free.

EXAMPLE 8

[0072] According to the general procedure above, 5 mL 2-hydroxyethyl methacrylate, 90 L diethyl bromomalonate, 100 mg 1,3-dimethylbarbituric acid and 250 L Eosin Yellow disodium salt (0.05 M in MeOH) were mixed and irradiated for 10-30 minutes via an green light emitting LED. Afterwards, the coating was yellow, transparent tack-free.

EXAMPLE 9

[0073] According to the general procedure above, 5 mL 2-hydroxyethyl methacrylate, 90 L diethyl bromomalonate, 100 mg 1,3-dimethylbarbituric acid and 250 L Fluorescein disodium salt (0.05 M in MeOH) were mixed and irradiated for 10-30 minutes via a blue light emitting LED. Afterwards, the coating was yellow, transparent tack-free.

EXAMPLE 10

[0074] According to the general procedure above, 5 mL 2-hydroxyethyl methacrylate, 60 L 1,4-dibromo-2,3-butandione, 100 mg 1,3-dimethylbarbituric acid and 250 L Fluorescein disodium salt (0.05 M in MeOH) were mixed and irradiated for 10-30 minutes via a blue light emitting LED. Afterwards, the coating was yellow, transparent tack-free.

EXAMPLE 11

[0075] According to the general procedure above, 5 mL 2-hydroxyethyl methacrylate, 25 mg 2-bromo-1,3-indandione, 65 mg 2,2-dimethyl-1,3-dioxane-4,6-dione and 250 L Fluorescein disodium salt (0.05 M in MeOH) were mixed and irradiated for 10-30 minutes via a blue light emitting LED. Afterwards, the coating was yellow, transparent tack-free.

EXAMPLE 12

[0076] According to the general procedure above, 5 mL ON UVA 421, 10 mg 2,2,4-tribromoacetophenone and 50 L Eosin Yellow disodium salt (0.05 M in MeOH) were mixed and irradiated for 10-30 minutes via a green light emitting LED. Afterwards, the coating was yellow, transparent tack-free.

EXAMPLE 13

[0077] According to the general procedure above, 5 mL 2-hydroxyethyl methacrylate, 100 mg 5,5-dibromomeldrum's acid, 50 mg 1,3-dimethylbarbituric acid and 10 L Eosin Yellow disodium salt (0.05 M in MeOH) were mixed and irradiated for 10-30 minutes via a green light emitting LED. Afterwards, the coating was colorless, transparent tack-free.

EXAMPLE 14

[0078] According to the general procedure above, 10 mL 2-hydroxyethyl methacrylate, 200 mg 5,5-dibromomeldrum's acid, 260 mg 1,3-dimethylbarbituric acid, 25 g SIKRON 3000, 18 mg BYK-UV-3500 and 500 L Eosin Yellow disodium salt (0.05 M in MeOH) were mixed and irradiated for 30 minutes via a green light emitting LED. Afterwards, the coating was yellow and tack-free.

EXAMPLE 15

[0079] According to the general procedure above, a mixture of 0.5 mL 2-hydroxyethyl methacrylate, 7 mL pentaerythritol tetraacrylate, 2.5 mL pentaerythritol pentaacrylate and 200 mg 5,5-dibromomeldrum's acid, 260 mg 1,3-dimethylbarbituric acid, 5 g SIKRON 3000, 18 mg BYK-UV-3500, and 500 L Eosin Yellow disodium salt (0.05 M in MeOH) were mixed and irradiated for 30 minutes via a green light emitting LED. Afterwards, the coating was yellow and tack-free.

EXAMPLE 16

[0080] According to the general procedure above, a mixture of 10 mL 2-hydroxyethyl methacrylate, 200 mg 5,5-dibromomeldrum's acid, 260 mg 1,3-dimethylbarbituric acid, 0.5-2.5 g CRENOX CR-435, 18 mg BYK-UV-3500, and 500 L Eosin Yellow disodium salt (0.05 M in MeOH) were mixed and irradiated for 30 minutes via a green light emitting LED. Afterwards, the coating was yellow and tack-free.

EXAMPLE 17

[0081] According to the general procedure above, a mixture of 0.25 mL 2-hydroxyethyl methacrylate, 3.5 mL pentaerythritol tetraacrylate, 1.25 mL pentaerythritol pentaacrylate and 200 mg 5,5-dibromomeldrum's acid, 260 mg 1,3-dimethylbarbituric acid, 5 g SIKRON 3000, 18 mg BYK-UV-3500 and 500 L Eosin Yellow disodium salt (0.05 M in MeOH) were mixed, applied on a cementeous surface (157.5 cm) and irradiated for 30 minutes via a green light emitting LED. Afterwards, the coating was yellow and tack-free.

EXAMPLE 18

[0082] According to the general procedure above, 5 mL 2-hydroxyethyl methacrylate, 500 mg poly(BMA-co-iBMA), 100 mg 5,5-dibromomeldrum's acid, 260 mg 1,3-dimethylbarbituric acid and 200 L Eosin Yellow disodium salt (0.05 M in MeOH) were mixed, applied on a cementeous surface (157.5 cm) and irradiated for 30 minutes via a green light emitting LED. Afterwards, the coating was yellow and tack-free.

EXAMPLE 19

[0083] According to the general procedure above, 0.25 mL 2-hydroxyethyl methacrylate and 4.75 mL tetrahydrofurfuryl methacrylate, 100 mg 5,5-dibromomeldrum's acid, 260 mg 1,3-dimethylbarbituric acid, 100 L Eosin Yellow disodium salt (0.05 M in MeOH) were mixed and applied on a glass surface (1010 cm). Another untreated glass surface was put on the coated surface and the glasses irradiated for 30 minutes via a green light emitting LED. Afterwards, the coating was transparent and the glasses couldn't be removed by hand. The glued glass was put in a Q-Sun machine (Xenon-Light with Daylight-Filter 0.68 W/m.sup.2, BlackPanel-Temp. 67 C. surface, air-temperature 40 C., humidity 50% r.H) and monitored for 14 days (UV-VIS-measurements). The VIS-region of the spectra (>360 nm) showed no changes, the glasses glued together and could not be detached from each other and showed transparency and colorlessness.

EXAMPLE 20

[0084] According to the general procedure above, 0.25 mL 2-hydroxyethyl methacrylate, 4.75 mL pentaerythritol tetraacrylate, 100 mg 5,5-dibromomeldrum's acid, 260 mg 1,3-dimethylbarbituric acid, 100 L Eosin Yellow disodium salt (0.05 M in MeOH) were mixed and applied on a glass surface (1010 cm). Another untreated glass surface was put on the coated surface and the glasses irradiated for 30 minutes via a green light emitting LED. Afterwards, the coating was transparent and the glasses couldn't be removed by hand. The glued glass was put in a Q-Sun machine (Xenon-Light with Daylight-Filter 0.68 W/m.sup.2, BlackPanel-Temp. 67 C. surface, air-temperature 40 C., humidity 50% r.H) and monitored for 14 days (UV-VIS-measurements). The VIS-region of the spectra (>360 nm) showed no changes, the glasses glued together and could not be detached from each other and showed transparency and colorlessness.

EXAMPLE 21

[0085] According to the general procedure above, 0.25 mL 2-hydroxyethyl methacrylate, 4.75 mL Trimethylolpropane trimethacrylate, 100 mg 5,5-dibromomeldrum's acid, 260 mg 1,3-dimethylbarbituric acid, 100 L Eosin Yellow disodium salt (0.05 M in MeOH) were mixed and applied on a glass surface (1010 cm). Another untreated glass surface was put on the coated surface and the glasses irradiated for 30 minutes via a green light emitting LED. Afterwards, the coating was transparent and the glasses couldn't remove by hand. The glued glass was put in a Q-Sun machine (Xenon-Light with Daylight-Filter 0.68 W/m.sup.2, BlackPanel-Temp. 67 C. surface, air-temperature 40 C., humidity 50% r.H) and monitored for 14 days (UV-VIS-measurements). The VIS-region of the spectra (>360 nm) showed no changes, the glasses glued together and could not be detached from each other and showed transparency and colorlessness.

EXAMPLE 22

[0086] According to the general procedure above, 0.25 mL 2-Hydroxyethyl methacrylate, 4.75 mL Diethylenglycole dimethacrylate, 100 mg 5,5-Dibromomeldrum's acid, 260 mg 1,3-Dimethylbarbituric acid, 100 L Eosin Yellow disodium salt (0.05M in MeOH) were mixed and applied on a glass surface (1010 cm). Another untreated glass surface was put on the coated surface and the glasses irradiated for 30 minutes via a green light emitting LED. Afterwards, the coating was transparent and the glasses couldn't remove by hand. The glued glass was put in a Q-Sun machine (Xenon-Light with Daylight-Filter 0.68 W/m.sup.2, BlackPanel-Temp. 67 C. surface, air-temperature 40 C., humidity 50% r.H) and monitored for 14 days (UV-VIS-measurements). The VIS-region of the spectra (>360 nm) showed no changes, the glasses glued together and could not be detached from each other and showed transparency and colorlessness.