Siloxane hard coating resin

Abstract

The present invention relates to a siloxane hard resin including alicyclic epoxy siloxane alone or a reactive monomer, which is prepared by condensation reaction of alkoxysilanes, and has a weight average molecular weight in the range of 1000 to 4000 and a molecular weight distribution of PDI 1.05 to 1.4. A siloxane hard cured article produced by photo- or thermal polymerization has high hardness by compact crosslinking of siloxane molecules having different molecular weights.

Claims

1. A hard coating composition consisting essentially of an alicyclic epoxy group-containing siloxane resin, which has a weight average molecular weight in the range of 1000 to 4000 and a molecular weight distribution of PDI 1.05 to 1.4, and a reactive monomer which is an oxetane monomer capable of reacting with the alicyclic epoxy group to form crosslinking in an amount of 1 to 100 parts by weight, based on 100 parts by weight of the siloxane resin, wherein the siloxane resin is prepared, in the presence of water and a catalyst, by hydrolysis and condensation of (i) alkoxysilane containing an alicyclic epoxy group and an alkoxy group represented by the following Chemical Formula 1 alone, or (ii) alkoxysilane having an alicyclic epoxy group and an alkoxy group represented by the following Chemical Formula 1 and one or more selected from the group consisting of tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltrimethoxysilane, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltripropoxysilane, 3-acryloxypropylmethylbis(trimethoxy)silane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltripropoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropyltripropoxysilane, N-(aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, and heptadecafluorodecyltrimethoxysilane:
R.sup.1.sub.nSi(OR.sup.2).sub.4-n[Chemical Formula 1] wherein R.sup.1 is a straight or branched C.sub.1 to C.sub.6 alkyl group containing an alicyclic epoxy group, the alicyclic epoxy group is a C.sub.3 to C.sub.6 cycloalkyl group having an epoxy group, R.sup.2 is a straight or branched C.sub.1 to C.sub.7 alkyl group, and n is an integer of 1 to 3.

2. The hard coating composition according to claim 1, wherein the alkoxysilane represented by Chemical Formula 1 is 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, or 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane.

3. The hard coating composition according to claim 1, wherein the oxetane monomer includes one or more of the oxetane group of the following Chemical Formula 4: ##STR00006##

4. The hard coating composition according to claim 3, wherein the oxetane monomer is one or more selected from the group consisting of 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyloxetane, xylene bis oxetane, and 3-ethyl-3[[[3-ethyloxetan-3-yl]methoxy]methyl]oxetane.

5. The hard coating composition according to claim 1, wherein the catalyst is selected from the group consisting of basic catalysts, and ion exchange resins, including ammonia, potassium hydroxide, sodium hydroxide, barium hydroxide, imidazole, Amberite IRA-400, IRA-67, and combinations thereof.

6. A method for producing a hard cured article by polymerization of the hard coating composition according to claim 1.

7. The method according to claim 6, wherein the polymerization includes a step of radiation or heating.

8. An optical film or sheet comprising the hard cured article that is produced by polymerization of the hard coating composition according to claim 1.

9. A hard coating composition consisting essentially of an alicyclic epoxy group-containing siloxane resin, which has a weight average molecular weight in the range of 1000 to 4000 and a molecular weight distribution of PDI 1.05 to 1.4, and an organic solvent in an amount of 0.1 to 10 parts by weight, based on 100 parts by weight of the siloxane resin, wherein the siloxane resin is prepared, in the presence of water and a catalyst, by hydrolysis and condensation of (i) alkoxysilane containing an alicyclic epoxy group and an alkoxy group represented by the following Chemical Formula 1 alone, or (ii) alkoxysilane having an alicyclic epoxy group and an alkoxy group represented by the following Chemical Formula 1 and one or more selected from the group consisting of tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltrimethoxysilane, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltripropoxysilane, 3-acryloxypropylmethylbis(trimethoxy)silane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltripropoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropyltripropoxysilane, N-(aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, and heptadecafluorodecyltrimethoxysilane:
R.sup.1.sub.nSi(OR.sup.2).sub.4-n[Chemical Formula 1] wherein R.sup.1 is a straight or branched C.sub.1 to C.sub.6 alkyl group containing an alicyclic epoxy group, the alicyclic epoxy group is a C3 to C6 cycloalkyl group having an epoxy group, R.sup.2 is a straight or branched C1 to C7 alkyl group, and n is an integer of 1 to 3.

10. A hard coating composition consisting essentially of an alicyclic epoxy group-containing siloxane resin, which has a weight average molecular weight in the range of 1000 to 4000 and a molecular weight distribution of PDI 1.05 to 1.4; an oxetane monomer capable of reacting with the alicyclic epoxy group to form crosslinking in an amount of 1 to 100 parts by weight, based on 100 parts by weight of the siloxane resin; and a polymerization initiator selected from the group consisting of onium salts, organometallic salts, amines, and imidazoles in an amount of 0.1 to 10 parts by weight, based on 100 parts by weight of the siloxane resin, wherein the siloxane resin is prepared, in the presence of water and a catalyst, by hydrolysis and condensation of (i) alkoxysilane containing an alicyclic epoxy group and an alkoxy group represented by the following Chemical Formula 1 alone, or (ii) alkoxysilane having an alicyclic epoxy group and an alkoxy group represented by the following Chemical Formula 1 and one or more selected from the group consisting of tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltrimethoxysilane, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltripropoxysilane, 3-acryloxypropylmethylbis(trimethoxy)silane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltripropoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropyltripropoxysilane, N-(aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, and heptadecafluorodecyltrimethoxysilane:
R.sup.1.sub.nSi(OR.sup.2).sub.4-n[Chemical Formula 1] wherein R.sup.1 is a straight or branched C.sub.1 to C.sub.6 alkyl group containing an alicyclic epoxy group, the alicyclic epoxy group is a C3 to C6 cycloalkyl group having an epoxy group, R.sup.2 is a straight or branched C1 to C7 alkyl group, and n is an integer of 1 to 3.

11. A hard coating composition consisting essentially of an alicyclic epoxy group-containing siloxane resin, which has a weight average molecular weight in the range of 1000 to 4000 and a molecular weight distribution of PDI 1.05 to 1.4; an oxetane monomer capable of reacting with the alicyclic epoxy group to form crosslinking in an amount of 1 to 100 parts by weight, based on 100 parts by weight of the siloxane resin; and one or more additives selected from the group consisting of an organic solvent, an antioxidant, a leveling agent, and a coating control agent, wherein the siloxane resin is prepared, in the presence of water and a catalyst, by hydrolysis and condensation of (i) alkoxysilane containing an alicyclic epoxy group and an alkoxy group represented by the following Chemical Formula 1 alone, or (ii) alkoxysilane having an alicyclic epoxy group and an alkoxy group represented by the following Chemical Formula 1 and one or more selected from the group consisting of tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltrimethoxysilane, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltripropoxysilane, 3-acryloxypropylmethylbis(trimethoxy)silane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltripropoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropyltripropoxysilane, N-(aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, and heptadecafluorodecyltrimethoxysilane:
R.sup.1.sub.nSi(OR.sup.2).sub.4-n[Chemical Formula 1] wherein R.sup.1 is a straight or branched C.sub.1 to C.sub.6 alkyl group containing an alicyclic epoxy group, the alicyclic epoxy group is a C3 to C6 cycloalkyl group having an epoxy group, R2 is a straight or branched C1 to C7 alkyl group, and n is an integer of 1 to 3.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a graph which is obtained by measuring molecular weights of siloxane hard resins having an alicyclic epoxy group according to Examples 1, 2, and 3 of the present invention using a Matrix-Assisted Laser Desorption Ionization Mass Spectrometer; and

(2) FIG. 2 is a graph which is obtained by measuring molecular weights of siloxane resins having an alicyclic epoxy group according to Examples 3, 4, and 5 of the present invention using a Matrix-Assisted Laser Desorption Ionization Mass Spectrometer.

(3) Hereinafter, the actions and the effects of the present invention will be explained in more detail via specific examples of the invention. However, these examples are merely illustrative of the present invention and the scope of the invention should not be construed to be defined thereby.

EXAMPLE 1

Photopolymerization

(4) 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECTMS, Gelest) and water (H.sub.2O, Sigma-Aldrich) were mixed at a ratio of 24.64 g:2.70 g (0.1 mol:0.15 mol), and then put into a 100 ml 2-neck flask. Thereafter, 0.05 ml of ammonia as a catalyst was added to the mixture, and stirred at 60 C. for 6 hours. The mixture was filtered using 0.45 m Teflon filter, thereby obtaining an alicyclic epoxy siloxane hard resin. The molecular weight of the alicyclic epoxy siloxane hard resin was measured using a Matrix-Assisted Laser Desorption Ionization Mass Spectrometer, and shown in the following FIG. 1. By using this measured value, it was confirmed that the alicyclic epoxy siloxane hard resin has a number average molecular weight of 1498, a weight average molecular weight of 1771, and PDI (M.sub.w/M.sub.n) of 1.18.

(5) Next, an aryl sulfonium hexafluoroantimonate salt as a polymerization initiator for photopolymerization was added in an amount of 2 parts by weight, based on the resultant resin. Then, 1.35 parts by weight of iso-octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 3.6 parts by weight of tris(nonylphenyl)phosphite were added as antioxidants to prevent oxidation due to the polymerization, based on the resultant resin.

(6) The siloxane hard resin composition was applied onto the surface of PET to have different thickness of 20, 40, and 60 m, and then exposed to a UV lamp at 365 nm wavelength for 1 minute for photo-curing. After photo-curing was completely finished, thermal treatment was performed at a temperature of 80 C. for 1 hour so as to produce a siloxane hard cured article.

EXAMPLE 2

Photopolymerization

(7) 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECTMS, Gelest) and water (H.sub.2O, Sigma-Aldrich) were mixed at a ratio of 24.64 g:2.70 g (0.1 mol:0.15 mol), and then put into a 100 ml 2-neck flask. Thereafter, 0.05 ml of ammonia as a catalyst was added to the mixture, and stirred at 60 C. for 6 hours. The mixture was filtered using 0.45 m Teflon filter, thereby obtaining an alicyclic epoxy siloxane hard resin. The molecular weight of the alicyclic epoxy siloxane hard resin was measured using a Matrix-Assisted Laser Desorption Ionization Mass Spectrometer, and shown in the following FIG. 1. By using this measured value, it was confirmed that the alicyclic epoxy siloxane hard resin has a number average molecular weight of 1498, a weight average molecular weight of 1771, and PDI (M.sub.w/M.sub.n) of 1.18.

(8) Next, 3-ethyl-3 [[[3-ethyloxetan-3-yl]methoxy]methyl]oxetane as a photopolymerizable monomer was added in an amount of 20 parts by weight, based on the resultant resin, and an aryl sulfonium hexafluoroantimonate salt as a polymerization initiator for photopolymerization was added in an amount of 2 parts by weight, based on the mixed resin. Then, 1.35 parts by weight of iso-octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 3.6 parts by weight of tris(nonylphenyl) phosphite were added as antioxidants to prevent oxidation due to the polymerization, based on the resultant resin.

(9) The siloxane hard resin composition was applied onto the surface of PET to have different thickness of 20, 40, and 60 m, and then exposed to a UV lamp at 365 nm wavelength for 1 minute for photo-curing. After photo-curing was completely finished, thermal treatment was performed at a temperature of 80 C. for 1 hour so as to produce a siloxane hard cured article.

EXAMPLE 3

Thermal Polymerization

(10) 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECTMS, Gelest) and water (H.sub.2O, Sigma-Aldrich) were mixed at a ratio of 24.64 g:2.70 g (0.1 mol:0.15 mol), and then put into a 100 ml 2-neck flask. Thereafter, 0.05 ml of ammonia as a catalyst was added to the mixture, and stirred at 60 C. for 6 hours. The mixture was filtered using 0.45 m Teflon filter, thereby obtaining an alicyclic epoxy siloxane hard resin. The molecular weight of the alicyclic epoxy siloxane hard resin was measured using a Matrix-Assisted Laser Desorption Ionization Mass Spectrometer, and shown in the following FIG. 1. By using this measured value, it was confirmed that the alicyclic epoxy siloxane hard resin has a number average molecular weight of 1498, a weight average molecular weight of 1771, and PDI (M.sub.w/M.sub.n) of 1.18.

(11) Next, 4-methyl-1,2-cyclohexene dicarboxylic anhydride as a thermal polymerizable monomer was added in an amount of 90 parts by weight, based on the resultant resin, and 2-ethyl-4-methylimidazole as a polymerization initiator for thermal polymerization was added in an amount of 2 parts by weight, based on the mixed resin. Then, 1.35 parts by weight of iso-octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 3.6 parts by weight of tris(nonylphenyl)phosphite were added as antioxidants to prevent oxidation due to the polymerization, based on the resultant resin.

(12) The siloxane hard resin composition was applied onto the surface of PET to have different thickness of 20, 40, and 60 m, and thermal treatment was performed at a temperature of 80 C. for 3 hours so as to produce a siloxane hard cured article.

EXAMPLE 4

Photopolymerization

(13) 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECTMS, Gelest) and water (H.sub.2O, Sigma-Aldrich) were mixed at a ratio of 24.64 g:2.70 g (0.1 mol:0.15 mol), and then put into a 100 ml 2-neck flask. Thereafter, 6.1 g of Amberite IRA-400 as a catalyst was added to the mixture, and stirred at 60 C. for 24 hours. The mixture was filtered using 0.45 m Teflon filter, thereby obtaining an alicyclic epoxy siloxane hard resin. The molecular weight of the alicyclic epoxy siloxane hard resin was measured using a Matrix-Assisted Laser Desorption Ionization Mass Spectrometer, and shown in the following FIG. 2. By using this measured value, it was confirmed that the alicyclic epoxy siloxane hard resin has a number average molecular weight of 2217, a weight average molecular weight of 2525, and PDI (M.sub.w/M.sub.n) of 1.14.

(14) Next, an aryl sulfonium hexafluoroantimonate salt as a polymerization initiator for photopolymerization was added in an amount of 2 parts by weight, based on the mixed resin. Then, 1.35 parts by weight of iso-octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 3.6 parts by weight of tris(nonylphenyl)phosphite were added as antioxidants to prevent oxidation due to the polymerization, based on the resultant resin.

(15) The siloxane hard resin composition was applied onto the surface of PET to have different thickness of 20, 40, and 60 m, and then exposed to a UV lamp at 365 nm wavelength for 1 minute for photo-curing. After photo-curing was completely finished, thermal treatment was performed at a temperature of 80 C. for 1 hour so as to produce a siloxane hard cured article.

EXAMPLE 5

Photopolymerization

(16) 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECTMS, Gelest) and water (H.sub.2O, Sigma-Aldrich) were mixed at a ratio of 24.64 g:2.70 g (0.1 mol:0.15 mol), and then put into a 100 ml 2-neck flask. Thereafter, 6.1 g of Amberite IRA-400 as a catalyst was added to the mixture, and stirred at 60 C. for 24 hours. The mixture was filtered using 0.45 m Teflon filter, thereby obtaining an alicyclic epoxy siloxane hard resin. The molecular weight of the alicyclic epoxy siloxane hard resin was measured using a Matrix-Assisted Laser Desorption Ionization Mass Spectrometer, and shown in the following FIG. 2. By using this measured value, it was confirmed that the alicyclic epoxy siloxane hard resin has a number average molecular weight of 2217, a weight average molecular weight of 2525, and PDI (M.sub.w/M.sub.n) of 1.14.

(17) Next, 3-ethyl-3 [[[3-ethyloxetan-3-yl]methoxy]methyl]oxetane as a photopolymerizable monomer was added in an amount of 20 parts by weight, based on the resultant resin, and an aryl sulfonium hexafluoroantimonate salt as a polymerization initiator for photopolymerization was added in an amount of 2 parts by weight, based on the mixed resin. Then, 1.35 parts by weight of iso-octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 3.6 parts by weight of tris(nonylphenyl) phosphite were added as antioxidants to prevent oxidation due to the polymerization, based on the resultant resin.

(18) The siloxane hard resin composition was applied onto the surface of PET to have different thickness of 20, 40, and 60 m, and then exposed to a UV lamp at 365 nm wavelength for 1 minute for photo-curing. After photo-curing was completely finished, thermal treatment was performed at a temperature of 80 C. for 1 hour so as to produce a siloxane hard cured article.

EXAMPLE 6

Thermal Polymerization

(19) 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECTMS, Gelest) and water (H.sub.2O, Sigma-Aldrich) were mixed at a ratio of 24.64 g:2.70 g (0.1 mol:0.15 mol), and then put into a 100 ml 2-neck flask. Thereafter, 6.1 g of Amberite IRA-400 as a catalyst was added to the mixture, and stirred at 60 C. for 24 hours. The mixture was filtered using 0.45 m Teflon filter, thereby obtaining an alicyclic epoxy siloxane hard resin. The molecular weight of the alicyclic epoxy siloxane hard resin was measured using a Matrix-Assisted Laser Desorption Ionization Mass Spectrometer, and shown in the following FIG. 2. By using this measured value, it was confirmed that the alicyclic epoxy siloxane hard resin has a number average molecular weight of 2217, a weight average molecular weight of 2525, and PDI (M.sub.w/M.sub.n) of 1.14.

(20) Next, 4-methyl-1,2-cyclohexenedicarboxylic anhydride as a thermal polymerizable monomer was added in an amount of 90 parts by weight, based on the resultant resin, and 2-ethyl-4-methylimidazole as a polymerization initiator for thermal polymerization was added in an amount of 2 parts by weight, based on the mixed resin. Then, 1.35 parts by weight of iso-octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 3.6 parts by weight of tris(nonylphenyl)phosphite were added as antioxidants to prevent oxidation due to the polymerization, based on the resultant resin.

(21) The siloxane hard resin composition was applied onto the surface of PET to have different thickness of 20, 40, and 60 m, and then thermal treatment was performed at a temperature of 80 C. for 3 hours so as to produce a siloxane hard cured article.

EXAMPLE 7

Photopolymerization

(22) 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECTMS, Gelest) and phenyltrimethoxysilane (PTMS, Gelest) were mixed at a ratio of 23.41 g:0.99 g (0.95 mol:0.05 mol), and 2.70 g (0.15 mol based on 0.1 mol of total silane) of water (H.sub.2O, Sigma-Aldrich) was added thereto, and then the mixture was put into a 100 ml 2-neck flask. Thereafter, 0.05 ml of ammonia as a catalyst was added to the mixture, and stirred at 60 C. for 6 hours. The mixture was filtered using 0.45 m Teflon filter, thereby obtaining an alicyclic epoxy siloxane hard resin. The molecular weight of the alicyclic epoxy siloxane hard resin was measured using a Matrix-Assisted Laser Desorption Ionization Mass Spectrometer. By using this measured value, it was confirmed that the alicyclic epoxy siloxane hard resin has a number average molecular weight of 1392, a weight average molecular weight of 1758, and PDI (M.sub.w/M.sub.n) of 1.26.

(23) Next, 3-ethyl-3[[[3-ethyloxetan-3-yl]methoxy]methyl]oxetane as a photopolymerizable monomer was added in an amount of 20 parts by weight, based on the resultant resin, and an aryl sulfonium hexafluoroantimonate salt as a polymerization initiator for photopolymerization was added in an amount of 2 parts by weight, based on the mixed resin. Then, 1.35 parts by weight of iso-octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 3.6 parts by weight of tris(nonylphenyl) phosphite were added as antioxidants to prevent oxidation due to the polymerization, based on the resultant resin.

(24) The siloxane hard resin composition was applied onto the surface of PET to have different thickness of 20, 40, and 60 m, and then exposed to a UV lamp at 365 nm wavelength for 1 minute for photo-curing. After photo-curing was completely finished, thermal treatment was performed at a temperature of 80 C. for 1 hour so as to produce a siloxane hard cured article.

EXAMPLE 8

Thermal Polymerization

(25) 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECTMS, Gelest) and phenyltrimethoxysilane (PTMS, Gelest) were mixed at a ratio of 23.41 g:0.99 g (0.95 mol:0.05 mol), and 2.70 g (0.15 mol based on 0.1 mol of total silane) of water (H.sub.2O, Sigma-Aldrich) was added thereto, and then the mixture was put into a 100 ml 2-neck flask. Thereafter, 0.05 ml of ammonia as a catalyst was added to the mixture, and stirred at 60 C. for 6 hours. The mixture was filtered using 0.45 m Teflon filter, thereby obtaining an alicyclic epoxy siloxane hard resin. The molecular weight of the alicyclic epoxy siloxane hard resin was measured using a Matrix-Assisted Laser Desorption Ionization Mass Spectrometer. By using this measured value, it was confirmed that the alicyclic epoxy siloxane hard resin has a number average molecular weight of 1392, a weight average molecular weight of 1758, and PDI (M.sub.w/M.sub.n) of 1.26.

(26) Next, 4-methyl-1,2-cyclohexenedicarboxylic anhydride as a thermal polymerizable monomer was added in an amount of 90 parts by weight, based on the resultant resin, and 2-ethyl-4-methylimidazole as a polymerization initiator for thermal polymerization was added in an amount of 2 parts by weight, based on the mixed resin. Then, 1.35 parts by weight of iso-octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 3.6 parts by weight of tris(nonylphenyl)phosphite were added as antioxidants to prevent oxidation due to the polymerization, based on the resultant resin.

(27) The siloxane hard resin composition was applied onto the surface of PET to have different thickness of 20, 40, and 60 m, and then thermal treatment was performed at a temperature of 80 C. for 3 hours so as to produce a siloxane hard cured article.

EXAMPLE 9

Photopolymerization

(28) 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECTMS, Gelest) and (heptadecafluoro-1,1,2,2-tetrahydrodecyl)trimethoxysilane (PFAS, Gelest) were mixed at a ratio of 24.15 g: 1.14 g (0.98 mol: 0.02 mol), and 2.70 g (0.15 mol based on 0.1 mol of total silane) of water (H.sub.2O, Sigma-Aldrich) was added thereto, and then the mixture was put into a 100 ml 2-neck flask. Thereafter, 0.05 ml of ammonia as a catalyst was added to the mixture, and stirred at 60 C. for 6 hours. The mixture was filtered using 0.45 m Teflon filter, thereby obtaining an alicyclic epoxy siloxane hard resin. The molecular weight of the alicyclic epoxy siloxane hard resin was measured using a Matrix-Assisted Laser Desorption Ionization Mass Spectrometer. By using this measured value, it was confirmed that the alicyclic epoxy siloxane hard resin has a number average molecular weight of 1979, a weight average molecular weight of 2507, and PDI (M.sub.w/M.sub.n) of 1.27.

(29) Next, 3-ethyl-3 [[[3-ethyloxetan-3-yl]methoxy]methyl]oxetane as a photopolymerizable monomer was added in an amount of 20 parts by weight, based on the resultant resin, and an aryl sulfonium hexafluoroantimonate salt as a polymerization initiator for photopolymerization was added in an amount of 2 parts by weight, based on the mixed resin. Then, 1.35 parts by weight of iso-octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 3.6 parts by weight of tris(nonylphenyl) phosphite were added as antioxidants to prevent oxidation due to the polymerization, based on the resultant resin.

(30) The siloxane hard resin composition was applied onto the surface of PET to have different thickness of 20, 40, and 60 m, and then exposed to a UV lamp at 365 nm wavelength for 1 minute for photo-curing. After photo-curing was completely finished, thermal treatment was performed at a temperature of 80 C. for 1 hour so as to produce a siloxane hard cured article.

EXAMPLE 10

Thermal Polymerization

(31) 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECTMS, Gelest) and (heptadecafluoro-1,1,2,2-tetrahydrodecyl)trimethoxysilane (PFAS, Gelest) were mixed at a ratio of 24.15 g: 1.14 g (0.98 mol: 0.02 mol), and 2.70 g (0.15 mol based on 0.1 mol of total silane) of water (H.sub.2O, Sigma-Aldrich) was added thereto, and then the mixture was put into a 100 ml 2-neck flask. Thereafter, 0.05 ml of ammonia as a catalyst was added to the mixture, and stirred at 60 C. for 6 hours. The mixture was filtered using 0.45 m Teflon filter, thereby obtaining an alicyclic epoxy siloxane hard resin. The molecular weight of the alicyclic epoxy siloxane hard resin was measured using a Matrix-Assisted Laser Desorption Ionization Mass Spectrometer. By using this measured value, it was confirmed that the alicyclic epoxy siloxane hard resin has a number average molecular weight of 1979, a weight average molecular weight of 2507, and PDI (M.sub.w/M.sub.n) of 1.27.

(32) Next, 4-methyl-1,2-cyclohexenedicarboxylic anhydride as a thermal polymerizable monomer was added in an amount of 90 parts by weight, based on the resultant resin, and 2-ethyl-4-methylimidazole as a polymerization initiator for thermal polymerization was added in an amount of 2 parts by weight, based on the mixed resin. Then, 1.35 parts by weight of iso-octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 3.6 parts by weight of tris(nonylphenyl)phosphite were added as antioxidants to prevent oxidation due to the polymerization, based on the resultant resin.

(33) The siloxane hard resin composition was applied onto the surface of PET to have different thickness of 20, 40, and 60 m, and then thermal treatment was performed at a temperature of 80 C. for 3 hours so as to produce a siloxane hard cured article.

EXAMPLE 11

Photopolymerization

(34) 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECTMS, Gelest) and 3-(meth)acryloxypropyltrimethoxysilane (MPTS, Gelest) were mixed at a ratio of 23.41 g:1.24 g (0.95 mol:0.05 mol), and 2.70 g (0.15 mol based on 0.1 mol of total silane) of water (H.sub.2O, Sigma-Aldrich) was added thereto, and then the mixture was put into a 100 ml 2-neck flask. Thereafter, 0.05 ml of ammonia as a catalyst was added to the mixture, and stirred at 60 C. for 6 hours. The mixture was filtered using 0.45 m Teflon filter, thereby obtaining an alicyclic epoxy siloxane hard resin. The molecular weight of the alicyclic epoxy siloxane hard resin was measured using a Matrix-Assisted Laser Desorption Ionization Mass Spectrometer. By using this measured value, it was confirmed that the alicyclic epoxy siloxane hard resin has a number average molecular weight of 1563, a weight average molecular weight of 2014, and PDI (M.sub.w/M.sub.n) of 1.29.

(35) Next, 3-ethyl-3 [[[3-ethyloxetan-3-yl]methoxy]methyl]oxetane as a photopolymerizable monomer was added in an amount of 20 parts by weight, based on the resultant resin, and an aryl sulfonium hexafluoroantimonate salt as a polymerization initiator for photopolymerization was added in an amount of 2 parts by weight, based on the mixed resin. Then, 1.35 parts by weight of iso-octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 3.6 parts by weight of tris(nonylphenyl) phosphite were added as antioxidants to prevent oxidation due to the polymerization, based on the resultant resin.

(36) The siloxane hard resin composition was applied onto the surface of PET to have different thickness of 20, 40, and 60 m, and then exposed to a UV lamp at 365 nm wavelength for 1 minute for photo-curing. After photo-curing was completely finished, thermal treatment was performed at a temperature of 80 C. for 1 hour so as to produce a siloxane hard cured article.

EXAMPLE 12

Thermal Polymerization

(37) 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECTMS, Gelest) and 3-(meth)acryloxypropyltrimethoxysilane (MPTS, Gelest) were mixed at a ratio of 23.41 g:1.24 g (0.95 mol:0.05 mol), and 2.70 g (0.15 mol based on 0.1 mol of total silane) of water (H.sub.2O, Sigma-Aldrich) was added thereto, and then the mixture was put into a 100 ml 2-neck flask. Thereafter, 0.05 ml of ammonia as a catalyst was added to the mixture, and stirred at 60 C. for 6 hours. The mixture was filtered using 0.45 m Teflon filter, thereby obtaining an alicyclic epoxy siloxane hard resin. The molecular weight of the alicyclic epoxy siloxane hard resin was measured using a Matrix-Assisted Laser Desorption Ionization Mass Spectrometer. By using this measured value, it was confirmed that the alicyclic epoxy siloxane hard resin has a number average molecular weight of 1563, a weight average molecular weight of 2014, and PDI (M.sub.w/M.sub.n) of 1.29.

(38) Next, 4-methyl-1,2-cyclohexenedicarboxylic anhydride as a thermal polymerizable monomer was added in an amount of 90 parts by weight, based on the resultant resin, and 2-ethyl-4-methylimidazole as a polymerization initiator for thermal polymerization was added in an amount of 2 parts by weight, based on the mixed resin. Then, 1.35 parts by weight of iso-octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 3.6 parts by weight of tris(nonylphenyl)phosphite were added as antioxidants to prevent oxidation due to the polymerization, based on the resultant resin.

(39) The siloxane hard resin composition was applied onto the surface of PET to have different thickness of 20, 40, and 60 m, and then thermal treatment was performed at a temperature of 80 C. for 3 hours so as to produce a siloxane hard cured article.

(40) The weight average molecular weights and PDI values of the alicyclic epoxy siloxane hard resins obtained in Examples are summarized in the following Table 1.

(41) TABLE-US-00001 TABLE 1 Weight average Example molecular weight PDI 1, 2, 3 1771 1.18 4, 5, 6 2525 1.14 7, 8 1758 1.26 9, 10 2507 1.27 11, 12 2014 1.29

(42) In order to measure the surface hardness of the siloxane hard cured articles obtained in Examples, a pencil hardness tester was used in accordance with ASTM D3363, and the results are shown in the following Table 2.

(43) TABLE-US-00002 TABLE 2 Thickness of coating film on PET Example 20 m 40 m 60 m 1 8H 9H 9H 2 8H 8H 9H 3 3H 4H 4H 4 8H 9H 9H 5 8H 8H 9H 6 3H 4H 4H 7 8H 8H 9H 8 3H 4H 4H 9 7H 8H 9H 10 3H 3H 4H 11 7H 8H 9H 12 3H 3H 4H

(44) As shown in Table 2, the siloxane hard resin of the present invention has a weight average molecular weight in the range of 1000 to 4000 and a molecular weight distribution of PDI 1.05 to 1.4 through polymerization reaction of the alicyclic epoxy group, thereby providing a siloxane hard cured article with high hardness by the compactly crosslinked siloxane molecules. Owing to easy processability, it also has the suitable properties as a hard coating agent.

(45) Although the present invention has been described in connection with the exemplary embodiments, it will be apparent that the present invention is not limited to the above embodiments, various modifications may be made thereto, and those skilled in the art will envision other modifications within the scope and spirit of the present invention.

(46) While this invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.