METHOD FOR COATING GLASS CONTAINERS

Abstract

The present invention relates to a method for hard coating glass containers comprising the steps of: Providing a heated glass container; Applying a coating composition on the outer surface of the heated glass container; Annealing the applied coating composition onto the outer surface of the heated glass container to obtain a coated glass container; wherein the coating composition comprises a metal and/or metalloid alcoholate, such as an alcoholate of titanium(IV), zirconium (IV), aluminium (III), tantalum (V), silicon (IV) and/or germanium (IV), in a solvent with a boiling point above 90? C., a coated glass container coated with the method as described above or below and the use of a coating composition comprising a metal alcoholate in a solvent with a boiling point above 90? C. for increasing the hardness of a coated glass container.

Claims

1. A method for coating glass containers comprising: Providing a heated glass container; Applying a coating composition on the outer surface of the heated glass container; Annealing the applied coating composition onto the outer surface of the heated glass container to obtain a coated glass container; wherein the coating composition comprises a metal and/or metalloid alcoholate, wherein the metalloid alcoholate comprises an alcoholate of titanium(IV), zirconium (IV), aluminium (III), tantalum (V), silicon (IV) and/or germanium (IV), in a solvent with a boiling point above 90? C.

2. The method according to claim 1, wherein the coating composition further comprises a siloxane polymer comprising one or more monomers selected from i) silane monomers of formula (I) ##STR00011## wherein R.sup.1 is independently selected from hydrogen and a group comprising linear and branched alkyl, cycloalkyl, alkenyl, alkynyl, (alkyl)acrylate, epoxy, allyl, vinyl and aryl having 1 to 6 rings, and wherein the group is substituted or unsubstituted; X is independently a hydrolysable group or a hydrocarbon residue under the proviso that at least one X is a hydrolysable group; and a is an integer 0 to 3; ii) bi-silane monomers of formula (II) ##STR00012## wherein R.sup.1 and R.sup.2 are independently selected from hydrogen and a group consisting of linear or branched alkyl, cycloalkyl, alkenyl, alkynyl, (alkyl)acrylate, epoxy, allyl, vinyl and aryl having 1 to 6 rings, and wherein the group is substituted or unsubstituted; X.sup.1 and X.sup.2 are independently a hydrolysable group or a hydrocarbon residue under the proviso that at least one residue of X.sup.1 and X.sup.2 is a hydrolysable group; a is an integer of 0 to 2 and Y is a linking group selected from bivalent unsubstituted or substituted aliphatic and aromatic groups, such as alkylene, arylene, O-alkylene-O; O-arylene-O; alkylene-O-alkylene, arylene-O-arylene; alkylene-Z.sup.1C(?O)Z.sup.2-alkylene, arylene-Z.sup.1C(?O)Z.sup.2-arylene and O-alkylene-Z.sup.1C(?O)Z.sup.2-alkylene-O; O-arylene-Z.sup.1C(?O)Z.sup.2-arylene-O, wherein Z.sup.1 and Z.sup.2 are each selected from a direct bond or O; and mixtures thereof.

3. The method according to claim 1, wherein the coating composition further comprises one or more silane components selected from i) silane monomers of formula (I) ##STR00013## wherein R.sup.1 is independently selected from hydrogen and a group comprising linear and branched alkyl, cycloalkyl, alkenyl, alkynyl, (alkyl)acrylate, epoxy, allyl, vinyl and aryl having 1 to 6 rings, and wherein the group is substituted or unsubstituted; X is independently a hydrolysable group or a hydrocarbon residue under the proviso that at least one X is a hydrolysable group; and a is an integer 0 to 3; ii) bi-silane monomers of formula (II) ##STR00014## wherein R.sup.1 and R.sup.2 are independently selected from hydrogen and a group consisting of linear or branched alkyl, cycloalkyl, alkenyl, alkynyl, (alkyl)acrylate, epoxy, allyl, vinyl and aryl having 1 to 6 rings, and wherein the group is substituted or unsubstituted; X.sup.1 and X.sup.2 are independently a hydrolysable group or a hydrocarbon residue under the proviso that at least one residue of X.sup.1 and X.sup.2 is a hydrolysable group; a is an integer of 0 to 2 and Y is a linking group selected from bivalent unsubstituted or substituted aliphatic and aromatic groups, such as alkylene, arylene, O-alkylene-O; O-arylene-O; alkylene-O-alkylene, arylene-O-arylene; alkylene-Z.sup.1C(?O)Z.sup.2-alkylene, arylene-Z.sup.1C(?O)Z.sup.2-arylene and O-alkylene-Z.sup.1C(?O)Z.sup.2-alkylene-O; O-arylene-Z.sup.1C(?O)Z.sup.2-arylene-O, wherein Z.sup.1 and Z.sup.2 are each selected from a direct bond or O; and mixtures thereof.

4. The method according to claim 1, wherein the metal and/or metalloid alcoholate comprises alkyl alcoholates, wherein the alkyl alcoholates are selected from linear or branched C1 to C10-alkyl alcoholates and/or silane alcoholates, wherein the silane alcoholates are alcoholates of one or more silane components selected from i) silane monomers of formula (I) ##STR00015## wherein R.sup.1 is selected from hydrogen and a group comprising linear and branched alkyl, cycloalkyl, alkenyl, alkynyl, (alkyl)acrylate, epoxy, allyl, vinyl and aryl having 1 to 6 rings, and wherein the group is substituted or unsubstituted; X is independently a hydrolysable group or a hydrocarbon residue under the proviso that at least one X is a hydrolysable group; and a is an integer 0 to 3; ii) bi-silane monomers of formula (II) ##STR00016## wherein R.sup.1 and R.sup.2 are independently selected from hydrogen and a group consisting of linear or branched alkyl, cycloalkyl, alkenyl, alkynyl, (alkyl)acrylate, epoxy, allyl, vinyl and aryl having 1 to 6 rings, and wherein the group is substituted or unsubstituted; X.sup.1 and X.sup.2 are independently a hydrolysable group or a hydrocarbon residue under the proviso that at least one residue of X.sup.1 and X.sup.2 is a hydrolysable group; a is an integer of 0 to 2 and Y is a linking group selected from bivalent unsubstituted or substituted aliphatic and aromatic groups, such as alkylene, arylene, O-alkylene-O; O-arylene-O; alkylene-O-alkylene, arylene-O-arylene; alkylene-Z.sup.1C(?O)Z.sup.2-alkylene, arylene-Z.sup.1C(?O)Z.sup.2-arylene and O-alkylene-Z.sup.1C(?O)Z.sup.2-alkylene-O; O-arylene-Z.sup.1C(?O)Z.sup.2-arylene-O, wherein Z.sup.1 and Z.sup.2 are each selected from a direct bond or O; and mixtures thereof.

5. The method according to claim 1, further comprising the following steps for preparing the coating composition: Solving the metal and/or metalloid alcoholate in a solvent with a boiling point above 90? C. to obtain the coating composition.

6. The method according to claim 1, further comprising the following steps for preparing the coating composition: Providing a solution of one or more silane components selected from i) silane monomers of formula (I) ##STR00017## wherein R.sup.1 is selected from hydrogen and a group comprising linear and branched alkyl, cycloalkyl, alkenyl, alkynyl, (alkyl)acrylate, epoxy, allyl, vinyl and aryl having 1 to 6 rings, and wherein the group is substituted or unsubstituted; X is independently a hydrolysable group or a hydrocarbon residue under the proviso that at least one X is a hydrolysable group; and a is an integer 0 to 3; ii) bi-silane monomers of formula (II) ##STR00018## wherein R.sup.1 and R.sup.2 are independently selected from hydrogen and a group consisting of linear or branched alkyl, cycloalkyl, alkenyl, alkynyl, (alkyl)acrylate, epoxy, allyl, vinyl, alkoxy and aryl having 1 to 6 rings, and wherein the group is substituted or unsubstituted; and Y is a linking group selected from bivalent unsubstituted or substituted aliphatic and aromatic groups, such as alkylene, arylene, O-alkylene-O; O-arylene-O; alkylene-O-alkylene, arylene-O-arylene; alkylene-Z.sup.1C(?O)Z.sup.2-alkylene, arylene-Z.sup.1C(?O)Z.sup.2-arylene and O-alkylene-Z.sup.1C(?O)Z.sup.2-alkylene-O; O-arylene-Z.sup.1C(?O)Z.sup.2-arylene-O, wherein Z.sup.1 and Z.sup.2 are each selected from a direct bond or O; and iii) mixtures thereof in a first solvent having a boiling point of not more than 85? C.; at least partially hydrolysing and polymerizing the silane components in the presence of water and an acidic catalyst to obtain a solution comprising siloxane polymer; adding linear or branched C1 to C10-alkyl metal and/or metalloid alcoholate to the solution comprising siloxane polymer; changing the first solvent to the solvent with a boiling point above 90? C. to obtain the coating composition.

7. The method according to claim 6, wherein the first solvent is selected from methanol, ethanol, isopropanol, tert-butanol, acetone, ethyl methyl ketone, tetrahydrofuran, hexane, cyclohexane, n-pentane or mixtures thereof.

8. The method according to claim 1, wherein the solvent with a boiling point above 90? C. comprises linear or branched C4 to C10 alkyl alcohols, 1-(isobutyryloxy)-2,2,4-trimethylpentan-3-yl hydrogencarbonate, propylene glycol propyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol n-propyl ether and/or 2,2,4-trimethyl-1,3-pentanediol-monoisobutyrate.

9. The method according to claim 1, wherein the solvent with a boiling point above 90? C. comprises 2,2,4-trimethyl-1,3-pentanediol-monoisobutyrate.

10. The method according to claim 1, wherein the coating composition is applied onto the outer surface of the heated glass container by spraying, blowing or vaporization.

11. The method according to claim 1, wherein the coating composition is annealed onto the outer surface of the heated glass container at a temperature of from 100? C. to 250? C. for 10 to 60 min.

12. A coated glass container coated with the method according to claim 1.

13. A coating composition comprising a metal and/or metalloid alcoholate in a solvent with a boiling point above 90? C. in a method for increasing the hardness of a coated glass container.

14. The coating composition according to claim 13 for one or more of increasing resistance to abrasion and scratching, reducing the gliding resistance, reducing the friction surface and/or increasing the optical properties such as improved reflection, improved transmission, reduced haze, of a coated glass container.

15. The coating composition of claim 13, wherein the solvent with a boiling point above 90? C. comprises 2,2,4-trimethyl-1,3-pentanediol-monoisobutyrate for increasing the slipping properties of the coated glass container.

Description

DETAILED DESCRIPTION OF THE INVENTION

Method

[0017] In one aspect the present invention relates to a method for coating glass containers comprising the steps of: [0018] Providing a heated glass container; [0019] Applying a coating composition on the outer surface of the heated glass container; [0020] Annealing the applied coating composition onto the outer surface of the heated glass container to obtain a coated glass container;

[0021] wherein the coating composition comprises a metal and/or metalloid alcoholate, such as an alcoholate of titanium(IV), zirconium (IV), aluminium (III), tantalum (V), silicon (IV) and/or germanium (IV) or mixtures thereof, in a solvent with a boiling point above 90? C.

[0022] In the present invention a metal and/or metalloid alcoholate is defined to be a metal and/or metalloid compound which comprises at least one alkoxide, such as from 1 to the valence of the metal or metalloid in the metal and/or metalloid compound.

[0023] The glass container to be coated can be any sort of glass container, which can be coated in a hot-end coating process, i.e. a glass container which can be coated at a temperature of at least 500? C.

[0024] The glass container can be a bottle, jar, can, drinking glassware, tableware, kitchenware, decorative glassware, laboratory glassware or others.

[0025] The glass container can be a container, which is open at the top, or a container, which is adapted to a top lid, such as a screw cap, a cap, a crown cork, a plug, a cork, a clip lock or others suitable for closing a glass container.

[0026] In one embodiment the heated glass container preferably has a temperature of at least 500? C., such as from 500? C. to 1500? C., preferably from 525? C. to 1200? C., more preferably from 550? C. to 1000? C. and most preferably from 575? C. to 900? C.

[0027] The temperature of the heated glass container thereby depends on the composition of the glass and its melting temperature. The heated glass container has a temperature below the melting temperature of its glass in order to avoid deterioration.

[0028] The heated glass container can be provided immediately after formation without an active cooling step. The heated glass container is thereby preferably provided immediately after formation before the annealing step. The coating method then relates to a hot-end coating method.

[0029] The heated glass container can also be a cold glass container, which is heated in at least one heating step. Preferably the cold glass container is heated in at least two heating steps. In a first heating step the cold glass container is preferably heated and annealed at a temperature of from 150? to 350? C., preferably 175? C. to 300? C. for a period of from 20 min to 300 min, preferably 30 min to 250 min.

[0030] In a second heating step the preheated and annealed glass container is then heated to a temperature of at least 500? C., such as from 500? C. to 1500? C., preferably from 525? C. to 1200? C., more preferably from 550? C. to 1000? C. and most preferably from 575? C. to 900? C.

[0031] In another embodiment the heated glass container preferably has a temperature of below 500? C., such as from 100? C. to below 500? C., preferably from 125? C. to 450? C., more preferably from 150? C. to 400? C. and most preferably from 175? C. to 350? C.

[0032] The heated glass container can be provided immediately after formation and the annealing step preferably without additional heating or cooling steps. The coating method the relates to a cold-end coating method.

[0033] The heated glass container can also be a cold glass container, which is heated in at least one heating step, preferably in one heating step.

[0034] On the outer surface of the heated glass container a coating composition is applied.

[0035] The coating composition is preferably applied by any suitable means for applying a coating onto a glass surface, such as by spraying, blowing or vaporization.

[0036] It is preferably preferred that the coating composition is applied by vaporization preferably as such that the heated glass container is subjected to the vapour of the coating composition. The vaporization thereby in practice can be accomplished by transporting the heated glass container through an area, which is saturated with the vapour of the coating composition.

[0037] The coating composition is preferably annealed onto the outer surface of the heated glass container at a temperature of from 100? C. to 250? C., more preferably from 125? C. to 230? C. and most preferably from 150? C. to 220? C.

[0038] The annealing time is preferably in the range of from 10 min to 60 min, more preferably from 15 min to 50 min, most preferably from 20 min to 45 min.

[0039] The coating on the other surface of the coated glass container is preferably in the range of from 10 nm to 500 nm, more preferably from 20 nm to 400 nm and most preferably from 30 nm to 300 nm.

[0040] The coating composition comprises a metal and/or metalloid alcoholate in a solvent with a boiling point above 90? C.

[0041] The metal and/or metalloid alcoholate is preferably selected from an alcoholate of titanium(IV), zirconium (IV), aluminium (III), tantalum (V), germanium (IV), silicon (IV) or mixtures thereof, more preferably an alcoholate of titanium (IV), zirconium (IV), aluminium (III), and silicon (IV) or mixtures thereof, most preferably an alcoholate of titanium(IV) and/or silicon (IV).

[0042] The metal and/or metalloid alkoholate can be any metal alcoholate which is suitable to hydrolyse to the accordant metal or metalloid oxide, such as TiO.sub.2, ZrO.sub.2, Al.sub.2O.sub.3, GeO.sub.2, Ta.sub.2O.sub.5, SiO.sub.2 or mixtures thereof, during the annealing step.

[0043] In the following the abbreviation metal alcoholate includes alcoholates of metals, such as the above mentioned alcoholates of titanium(IV), zirconium (IV), aluminium (III), tantalum (V), and metalloids, such as the above mentioned alcoholates of germanium (IV) and silicon (IV), and mixtures thereof.

[0044] The metal alkoholate can comprise the alkyl alcoholates are selected from linear or branched C1 to C10-alkyl alcoholates, preferably from linear or branched C1 to C6-alkyl alcoholates, more preferably from C1 to C4-alkyl alcoholates, such as methyl alcoholate, ethyl alcoholate, isopropyl alcoholate or tert-butyl alcoholate or mixtures thereof, preferably from isopropyl alcoholate or tert-butyl alcoholate and most preferably from isopropyl alcoholate.

[0045] The metal alcoholate can further comprise silane alcoholates, wherein the silane alcoholates are alcoholates of one or more silane components selected from [0046] i) silane monomers of formula (I)

##STR00001## [0047] wherein [0048] R.sup.1 is selected from hydrogen and a group comprising linear and branched alkyl, cycloalkyl, alkenyl, alkynyl, (alkyl)acrylate, epoxy, allyl, vinyl and aryl having 1 to 6 rings, and wherein the group is substituted or unsubstituted; [0049] X is independently a hydrolysable group or a hydrocarbon residue under the proviso that at least one X is a hydrolysable group; and [0050] a is an integer 0 to 3; [0051] ii) bi-silane monomers of formula (II)

##STR00002## [0052] wherein [0053] R.sup.1 and R.sup.2 are independently selected from hydrogen and a group consisting of linear or branched alkyl, cycloalkyl, alkenyl, alkynyl, (alkyl)acrylate, epoxy, allyl, vinyl and aryl having 1 to 6 rings, and wherein the group is substituted or unsubstituted; [0054] X.sup.1 and X.sup.2 are independently a hydrolysable group or a hydrocarbon residue under the proviso that at least one residue of X.sup.1 and X.sup.2 is a hydrolysable group; [0055] a is an integer of 0 to 2 [0056] and [0057] Y is a linking group selected from bivalent unsubstituted or substituted aliphatic and aromatic groups, such as alkylene, arylene, O-alkylene-O; O-arylene-O; alkylene-O-alkylene, arylene-O-arylene; alkylene-Z.sup.1C(?O)Z.sup.2-alkylene, arylene-Z.sup.1C(?O)Z.sup.2-arylene and O-alkylene-Z.sup.1C(?O)Z.sup.2-alkylene-O; O-arylene-Z.sup.1C(?O)Z.sup.2-arylene-O, wherein Z.sup.1 and Z.sup.2 are each selected from a direct bond or O; and

[0058] mixtures thereof.

[0059] The coating composition preferably is a solution of the coating composition. As a consequence a solvent with a boiling point above 90? C. is preferably suitable for solving the metal alcoholate and any other component in the coating composition. The solvent with a boiling point above 90? C. is preferably an organic solvent.

[0060] The solvent with a boiling point above 90? C. preferably comprises linear or branched C4 to C10 alkyl alcohols, 1-(isobutyryloxy)-2,2,4-trimethylpentan-3-yl hydrogencarbonate, propylene glycol propyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol n-propyl ether and/or 2,2,4-trimethyl-1,3-pentanediol-monoisobutyrate.

[0061] It is especially preferred that the solvent with a boiling point above 90? C. comprises 2,2,4-trimethyl-1,3-pentanediol-monoisobutyrate. The solvent with a boiling point above 90? C. can consist of 2,2,4-trimethyl-1,3-pentanediol-monoisobutyrate or can comprise 2,2,4-trimethyl-1,3-pentanediol-monoisobutyrate and another component, such as another solvent with a boiling point above 90? C. as described herein, and/or an acid, such as acetic acid.

[0062] When the solvent with a boiling point above 90? C. comprises 2,2,4-trimethyl-1,3-pentanediol-monoisobutyrate it has been found that slippage properties of the resultant coated glass container are improved.

[0063] It is preferred that the method of the invention comprises a further step for preparing the coating composition: [0064] Solving the metal alcoholate in a solvent with a boiling point above 90? C. to obtain the coating composition.

[0065] The coating composition preferably further comprises a siloxane polymer comprising one or more monomers selected from [0066] i) silane monomers of formula (I)

##STR00003## [0067] wherein [0068] R.sup.1 is independently selected from hydrogen and a group comprising linear and branched alkyl, cycloalkyl, alkenyl, alkynyl, (alkyl)acrylate, epoxy, allyl, vinyl and aryl having 1 to 6 rings, and wherein the group is substituted or unsubstituted; [0069] X is independently a hydrolysable group or a hydrocarbon residue; and [0070] a is an integer 0 to 3; [0071] ii) bi-silane monomers of formula (II)

##STR00004## [0072] wherein [0073] R.sup.1 and R.sup.2 are independently selected from hydrogen and a group consisting of linear or branched alkyl, cycloalkyl, alkenyl, alkynyl, (alkyl)acrylate, epoxy, allyl, vinyl and aryl having 1 to 6 rings, and wherein the group is substituted or unsubstituted; [0074] X.sup.1 and X.sup.2 are independently a hydrolysable group or a hydrocarbon residue under the proviso that at least one residue of X.sup.1 and X.sup.2 is a hydrolysable group; [0075] a is an integer of 0 to 2 [0076] and [0077] Y is a linking group selected from bivalent unsubstituted or substituted aliphatic and aromatic groups, such as alkylene, arylene, O-alkylene-O; O-arylene-O; alkylene-O-alkylene, arylene-O-arylene; alkylene-Z.sup.1C(?O)Z.sup.2-alkylene, arylene-Z.sup.1C(?O)Z.sup.2-arylene and O-alkylene-Z.sup.1C(?O)Z.sup.2-alkylene-O; O-arylene-Z.sup.1C(?O)Z.sup.2-arylene-O, wherein Z.sup.1 and Z.sup.2 are each selected from a direct bond or O; and

[0078] mixtures thereof.

[0079] The siloxane polymer can be a siloxane homopolymer, i.e. the siloxane polymer consists of one silane monomer or bi-silane monomer as defined herein.

[0080] The siloxane polymer can be a siloxane copolymer, i.e. the siloxane polymer comprises two or more, such as two to ten, preferably two to six, more preferably two to five silane monomers and/or bi-silane monomers as defined herein.

[0081] Additionally, the coating composition preferably further comprises one or more silane components selected from [0082] i) silane monomers of formula (I)

##STR00005## [0083] wherein [0084] R.sup.1 is independently selected from hydrogen and a group comprising linear and branched alkyl, cycloalkyl, alkenyl, alkynyl, (alkyl)acrylate, epoxy, allyl, vinyl and aryl having 1 to 6 rings, and wherein the group is substituted or unsubstituted; [0085] X is independently a hydrolysable group or a hydrocarbon residue; and [0086] a is an integer 0 to 3; [0087] ii) bi-silane monomers of formula (II)

##STR00006## [0088] wherein [0089] R.sup.1 and R.sup.2 are independently selected from hydrogen and a group consisting of linear or branched alkyl, cycloalkyl, alkenyl, alkynyl, (alkyl)acrylate, epoxy, allyl, vinyl and aryl having 1 to 6 rings, and wherein the group is substituted or unsubstituted; [0090] X.sup.1 and X.sup.2 are independently a hydrolysable group or a hydrocarbon residue; [0091] a is an integer of 0 to 2 [0092] and [0093] Y is a linking group selected from bivalent unsubstituted or substituted aliphatic and aromatic groups, such as alkylene, arylene, O-alkylene-O; O-arylene-O; alkylene-O-alkylene, arylene-O-arylene; alkylene-Z.sup.1C(?O)Z.sup.2-alkylene, arylene-Z.sup.1C(?O)Z.sup.2-arylene and O-alkylene-Z.sup.1C(?O)Z.sup.2-alkylene-O; O-arylene-Z.sup.1C(?O)Z.sup.2-arylene-O, wherein Z.sup.1 and Z.sup.2 are each selected from a direct bond or O; and [0094] mixtures thereof.

[0095] Preferably the silane components are defined the same way as the monomers of the siloxane polymer.

[0096] For the monomers of the siloxane polymer and the silane components the following preferred specifications apply:

[0097] For the silane monomer of formula (I)

[0098] X is independently a hydrolysable group or a hydrocarbon residue.

[0099] The hydrocarbon residue is in particular a linear or branched alkyl group.

[0100] The hydrolysable group hydrolysable group is in particular an alkoxy group. The alkoxy groups of the silane monomer is preferably selected from the group of radicals having the formula

##STR00007##

[0101] wherein R.sup.2 stands for a linear or branched alkyl group having 1 to 10, preferably 1 to 6 carbon atoms, and optionally exhibiting one or two substituents selected from the group of halogen, hydroxyl, vinyl, epoxy and allyl. Especially preferred are methoxy and ethoxy groups.

[0102] According to an embodiment, the silane monomer can be a tri- or tetraalkoxysilane.

[0103] In another embodiment the silane monomer does not comprise a hydrolysable group.

[0104] Particularly suitable silane monomers are selected from the group of triethoxysilane, tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, n-butyltriethoxysilane, n-hexyltriethoxysilane, n-octyltrimethylsilane, methyldiethoxyvinylsilane, dimethyldiethoxysilane, phenyltrimethoxysilane, dimethoxymethylphenylsilane, phenantrene-9-triethoxysilane, vinyltrimethoxysilane, (3-glycidyloxypropyl)trimethoxysilane, (3-glycidyloxypropyl)triethoxysilane, 3-trimethoxysilylpropylmethacrylate, aminopropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, acryloxypropyl-trimethoxysilane, allyltrimethoxysilane, epoxycyclohexylethyltrimethoxysilane, diphenylsilanediol, dimethyldimethoxysilane, 1-(2-(Trimethoxysilyl)ethyl)cyclohexane-3,4-epoxide, 1H, 1H, 2H, 2H-perfluorooctyltrimethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane, trimethoxy (3,3,3-trifluoropropyl)silane and combinations thereof.

[0105] Especially preferred are tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, n-hexyltriethoxysilane, n-octyltrimethylsilane, dimethoxymethylphenylsilane, (3-glycidyloxypropyl)trimethoxysilane, (3-glycidyloxypropyl)triethoxysilane, 3-trimethoxysilylpropylmethacrylate, allyltrimethoxysilane, 1H, 1H, 2H, 2H-perfluorooctyltrimethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane and combinations thereof.

[0106] Most preferred are methyltriethoxysilane, n-octyltrimethylsilane, 3-trimethoxysilylpropylmethacrylate, and combinations thereof.

[0107] For the bi-silane monomers of formula (II)

[0108] X.sup.1 and X.sup.2 are independently a hydrolysable group or a hydrocarbon residue.

[0109] The hydrocarbon residue is in particular a linear and branched alkyl group.

[0110] The hydrolysable group hydrolysable group is in particular an alkoxy group. The alkoxy groups of the bi-silane monomer is preferably selected from the group of radicals having the formula

##STR00008##

[0111] wherein R.sup.3 stands for a linear or branched alkyl group having 1 to 10, preferably 1 to 6 carbon atoms, and optionally exhibiting one or two substituents selected from the group of halogen, hydroxyl, vinyl, epoxy and allyl. Especially preferred are methoxy and ethoxy groups.

[0112] Y is a linking group selected from bivalent unsubstituted or substituted aliphatic and aromatic groups, such as alkylene, arylene, O-alkylene-O; O-arylene-O; alkylene-O-alkylene, arylene-O-arylene; alkylene-Z.sup.1C(?O)Z.sup.2-alkylene, arylene-Z.sup.1C(?O)Z.sup.2-arylene and O-alkylene-Z.sup.1C(?O)Z.sup.2-alkylene-O; O-arylene-Z.sup.1C(?O)Z.sup.2-arylene-O, wherein Z.sup.1 and Z.sup.2 are each selected from a direct bond or O.

[0113] In the bivalent alkylene groups and other similar aliphatic groups, the alkyl residue (or residue derived from an alkyl moiety) stands for 1 to 10, preferably 1 to 8, or 1 to 6 or even 1 to 4 carbon atoms, examples include ethylene and methylene and propylene.

[0114] Arylene stands for an aromatic bivalent group containing typically 1 to 3 aromatic rings, and 6 to 18 carbon atoms. Such groups are exemplified by phenylene (e.g. 1,4-phenylene and 1,3-phenylene groups) and biphenylene groups as well as naphthylene or anthracenylene groups.

[0115] The alkylene and arylene groups can optionally be substituted with 1 to 5 substituents selected from hydroxy, halo, vinyl, epoxy and allyl groups as well as alkyl, aryl and aralkyl groups.

[0116] The term phenyl includes substituted phenyls such as phenyltrialkoxy, in particular phenyltrimethoxy or triethoxy, and perfluorophenyl. The phenyl as well as other aromatic or alicyclic groups can be coupled directly to a silicon atom or they can be coupled to a silicon atom via a methylene or ethylene bridge.

[0117] Exemplary bi-silanes include 1,2-bis(trimethoxysilyl)methane, 1,2-bis(triethoxysilyl)methane, 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(triethoxysilyl)ethane, 1-(dimethoxymethylsilyl)-1-(trimethoxysilyl)methane, 1-(diethoxymethylsilyl)-1-(triethoxysilyl)methane, 1-(dimethoxymethylsilyl)-2-(trimethoxysilyl)ethane, 1-(diethoxymethylsilyl)-2-(triethoxysilyl)ethane, bis(dimethoxymethylsilyl)methane, bis(diethoxymethylsilyl)methane, 1,2-bis(dimethoxymethylsilyl)ethane, 1,2-bis(diethoxymethylsilyl)ethane, 1,2-bis(trimethoxysilyl)benzene, 1,2-bis(triethoxysilyl)benzene, 1,3-bis(trimethoxysilyl)benzene, 1,3-bis(triethoxysilyl)benzene, 1,4-bis(trimethoxysilyl)benzene, 1,4-bis(triethoxysilyl)benzene, 4,4-Bis(triethoxysilyl)-1,1-biphenyl; 1,4-Bis(triethoxysilyl)benzene; 1,3-Bis(triethoxysilyl)benzene and combinations thereof.

[0118] Especially preferred are 1,2-bis(trimethoxysilyl)methane, 1,2-bis(triethoxysilyl)methane, 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(triethoxysilyl)ethane and combinations thereof.

[0119] Mostly preferred are 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(triethoxysilyl)ethane and combinations thereof.

[0120] In the present context, the term bi-silane is used for designating a compound comprising two organic residues, in particular silicon containing residues, which are linked to the same atom(s). In case of two identical (or even symmetrical) organic residues, the term bis-silane is also used.

[0121] The siloxane polymer is preferably prepared by the steps comprising solving silane components selected from one or more silane monomer(s) and/or bi-silane monomer(s) in a solvent, at least partially hydrolysing and polymerizing the silane components in the presence of water and an acidic catalyst to obtain a solution comprising siloxane polymer.

[0122] The solvent is preferably selected from methanol, ethanol, isopropanol, tert-butanol, acetone, ethyl methyl ketone, tetrahydrofuran, propylene glycol methyl ether, propylene glycol methyl ether acetate, hexane, cyclohexane, n-pentane, toluene or mixtures thereof, more preferably from methanol, ethanol, isopropanol, tert-butanol or mixtures thereof, still more preferably from isopropanol and tert-butanol and most preferably from isopropanol.

[0123] The acidic catalyst is preferably aqueous acid e.g. nitric acid or hydrochloric acid or another mineral or organic acid.

[0124] Due to the presence of the acidic catalyst the water used in the hydrolysis step has typically a pH of less than 7, preferably less than 6, in particular less than 5.

[0125] Polymerization is preferably a condensation polymerization.

[0126] The hydrolysis and polymerization step preferably includes refluxing. A typical refluxing time is 2 h.

[0127] Additionally, the siloxane polymer in further step can be crosslinked, especially for increasing the molecular weight of the siloxane polymer.

[0128] The crosslinking preferably is induced by thermal or radiation initiation. For initiating crosslinking the polymer must comprise an active group which is capable of achieving cross-linking to adjacent siloxane polymer chains upon a thermal or radiation initiation. Exemplary active groups are epoxy, vinyl, allyl and methacrylate groups.

[0129] For radical initiation the presence of a radical initiator is necessary. Suitable radical initiators are organic peroxides or organic azo compound. Suitable radical initiators are e.g. azobisisobutyronitrile, azobis(2,4-dimethylvaleronitrile), 1,1-Azobis(cyclohexanecarbonitrile), 2,2-azobis(2-methylpropane), 4,4-azobis(4-cyanovaleric acid). Such radical initiators as well as other suitable radical initiators are well known in the art.

[0130] Exemplary radiation initiation is subjecting the mixture to UV light. Radical initiators and photoacid/base generators (both non-ionic and ionic and cationic and anionic) can be used as UV initiators. Such initiators are well known in the art.

[0131] In the siloxane polymer also free SiOH-groups can be protected with an end capping. Such an end capping can be obtained by a nucleophilic substitution reaction of an SiOH group of the siloxane polymer with silane components with a single hydrolysable group such as alkoxytrialkylsilanes or trialkylsilanemonohalides.

[0132] The alkyl groups are preferably selected from linear or branched alkyl groups having from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms.

[0133] The alkoxy group is preferably selected from C1 to C4 alkoxy groups, most preferably from methoxy and ethoxygroups.

[0134] The halide is preferably selected from chloride or bromide, most preferably chloride.

[0135] Especially preferred silane components for end capping are methoxytrimethylsilane, ethoxytrimethylsilane, methoxytriethylsilane, ethoxytriethylsilane, trimethylsilyl chloride, triethylsilyl chloride and mixtures thereof.

[0136] Mostly preferred are ethoxytrimethylsilane and trimethylsilyl chloride.

[0137] End-capping usually increases the chain length of the siloxane polymer, e.g. approximately doubles the chain length of the siloxane polymer.

[0138] Additionally end-capping of the remaining SiOH groups usually improves the shelf-life of the polysiloxane and improves its stability towards ageing processes (Journal of Applied Polymer Science, 2021, 138 (21), 50467).

[0139] The general conditions for preparing a siloxane polymer are generally known in the area and are exemplarily disclosed e.g. in WO 2009/068755 A1 or WO 2016/146896 A1.

[0140] In one preferred embodiment the coating composition comprises the metal alcoholate and the siloxane polymer in the solvent with a boiling point above 90? C. In said embodiment the coating composition can additionally comprise the one or more silane components as described herein.

[0141] In said embodiment the method of the invention can further comprise the following steps for preparing the coating composition: [0142] Providing a solution of one or more silane components selected from [0143] i) silane monomers of formula (I)

##STR00009## [0144] wherein [0145] R.sup.1 is selected from hydrogen and a group comprising linear and branched alkyl, cycloalkyl, alkenyl, alkynyl, (alkyl)acrylate, epoxy, allyl, vinyl and aryl having 1 to 6 rings, and wherein the group is substituted or unsubstituted; [0146] X is independently a hydrolysable group or a hydrocarbon residue under the proviso that at least one X is a hydrolysable group; and [0147] a is an integer 0 to 3; [0148] ii) bi-silane monomers of formula (II)

##STR00010## [0149] wherein [0150] R.sup.1 and R.sup.2 are independently selected from hydrogen and a group consisting of linear or branched alkyl, cycloalkyl, alkenyl, alkynyl, (alkyl)acrylate, epoxy, allyl, vinyl, alkoxy and aryl having 1 to 6 rings, and wherein the group is substituted or unsubstitued; and [0151] Y is a linking group selected from bivalent unsubstituted or substituted aliphatic and aromatic groups, such as alkylene, arylene, O-alkylene-O; O-arylene-O; alkylene-O-alkylene, arylene-O-arylene; alkylene-Z.sup.1C(?O)Z.sup.2-alkylene, arylene-Z.sup.1C(?O)Z.sup.2-arylene and O-alkylene-Z.sup.1C(?O)Z.sup.2-alkylene-O; O-arylene-Z.sup.1C(?O)Z.sup.2-arylene-O, wherein Z.sup.1 and Z.sup.2 are each selected from a direct bond or O; and [0152] mixtures thereof [0153] in a first solvent having a boiling point of not more than 85? C.; [0154] at least partially hydrolysing and polymerizing the silane components in the presence of water and an acidic catalyst to obtain a solution comprising siloxane polymer; [0155] adding linear or branched C1 to C10-alkyl metal alcoholate to the solution comprising siloxane polymer; [0156] changing the first solvent to the solvent with a boiling point above 90? C. to obtain the coating composition.

[0157] The first solvent is preferably selected from methanol, ethanol, isopropanol, tert-butanol, acetone, ethyl methyl ketone, tetrahydrofuran, hexane, cyclohexane, n-pentane or mixtures thereof, more preferably from methanol, ethanol, isopropanol, tert-butanol or mixtures thereof, still more preferably from isopropanol and tert-butanol and most preferably from isopropanol.

[0158] In one preferred embodiment the first solvent has the same chemical structure as the alkyl alcoholate of the metal alcoholate.

[0159] In said embodiment the coating composition can comprise the siloxane polymer and unreacted silane components. The unreacted silane components can be removed from the coating composition but are preferably left in the coating composition.

[0160] These unreacted silane components can react with the linear or branched C1 to C10-alkyl metal alcoholate in a transesterification reaction so that at least part of the linear or branched C1 to C10-alkyl alcoholates are exchanged by silane alcoholates. The resulting linear or branched C1 to C10-alkyl alcohols preferably have a boiling point of not more than 85? C. and are removed together with the first solvent.

[0161] The first solvent is preferably exchanged by the solvent with a boiling point above 90? C. by adding the solvent with a boiling point above 90? C. to the coating composition and heating the coating composition to a temperature above the boiling point of the first solvent but below the boiling point of the solvent with a boiling point above 90? C.

Coated Glass Container

[0162] According to another aspect, the present invention relates to coated glass container coated with the method as described above or below.

[0163] All aspects of the glass container or the method according to the invention as described herein apply to the coated glass container of said aspect of the invention.

[0164] Depending on the desired application the coating composition can be chosen to obtain one or more of the following properties:

[0165] Depending on the coating composition the coated glass container can show decorative effect such as a pearlescent effect. Such coated glass containers especially qualify for decorative applications such as decorative glassware or lifestyle products, such as perfume bottles or cosmetic glass jars or bottles.

[0166] The coated glass containers preferably show an outer surface with low visual defects, such as colour changes, dustiness, opaque spots, non-uniformities of the coating.

[0167] Additionally, the coated glass containers preferably show good optical properties such as a high light transmission, a high refractive index and low haze.

[0168] Further the coated glass containers preferably show a high scratch resistance, preferably either by the scratching test as described below or by scratching the coated glass container with steel wool.

[0169] Additionally, the coated glass containers preferably show a high slippage. Thereby, it has been found that the slippage can further be increased by addition of 2,2,4-trimethyl-1,3-pentanediol-monoisobutyrate to the solvent with a boiling point above 90? C.

[0170] The coated glass container preferably shows a low abrasion.

[0171] Preferably the coated glass container also shows and improved surface friction.

[0172] Further, the coated glass container preferably shows high water contact angles.

[0173] The coating can be applied as hot-end coating or cold-end coating and thus increases variability of the production process of the glass container.

[0174] Finally, by using a metal alcoholate instead of organic tin chlorides such as monobutyltin trichloride corrosion of metal caps can be significantly reduced. These metal alcoholates also have a low toxicity.

Use

[0175] In yet a further aspect the present invention relates to the use of a coating composition comprising a metal alcoholate in a solvent with a boiling point above 90? C. for increasing the hardness of a coated glass container.

[0176] All aspects of the glass container or the method according to the invention as described herein apply to the coated glass container of said aspect of the invention.

[0177] It is preferred that the solvent with a boiling point above 90? C. comprises 2,2,4-trimethyl-1,3-pentanediol-monoisobutyrate for increasing the slipping properties of the coated glass container.

[0178] The coating composition can also be used for increasing resistance to abrasion and scratching of the coated glass container.

[0179] Further, the coating composition can be used for reducing the gliding resistance, reducing the friction surface of a coated glass container.

[0180] The coating composition can also be used for increasing the optical properties such as improved reflection, improved transmission, reduced haze, of a coated glass container.

Experimental Section

[0181] The following Examples are included to demonstrate certain aspects and embodiments of the invention as described in the claims. It should be appreciated by those of skill in the art, however, that the following description is illustrative only and should not be taken in any way as a restriction of the invention.

[0182] In the description of the preparation of the coating compositions the following abbreviations are used: [0183] BTESE 1,2-Bis(triethoxysilyl)ethane [0184] MTEOS methyltriethoxysilane [0185] MEMO 3-trimethoxysilylpropylmethacrylate (commerically available as Dynasilan? MEMO) [0186] n-octylTMS n-octyltrimethylsilane [0187] IPA isopropanol [0188] BuOH n-butanol [0189] Texanol 2,2,4-Trimethyl-1,3-pentanediol monoisobutyrate [0190] Ti(iPropyl).sub.4 titanium tetraisopropoxide [0191] HNO.sub.3 nitric acid [0192] RT room temperature, about 23? C. [0193] Eq molar equivalents [0194] MBTC monobutyltin trichloride

Subjective Evaluation Methods

[0195] Visual inspection

[0196] The coated glass jar or bottle is visually inspected for any visual defects, such as colour changes, dustiness, opaque spots, non-uniformities of the coating (Leopard effect), etc.

[0197] The coated bottles are then classified in a three-stage categorization with [0198] 0=lots of defects, bad appearance [0199] 3=no defects, best results [0200] Slipping properties

[0201] Two bottles are gently slid against each other and the slippage of the coatings is categorized in a six-stage categorization. [0202] 0=slippage as experienced between two uncoated bottles [0203] 3=slippage as experienced between two hot coated bottles coated with a state-of-the-art MBTC coating (coating composition 17) [0204] 5=slippage as experienced between one hot coated bottle coated with a state-of-the-art MBTC coating (coating composition 17) and one cold coated bottle coated with a polyethylene wax coating [0205] Scratch resistance

[0206] Two bottles are forced to scratch against each other and the amount of observed scratches is categorized in a four-stage categorization. [0207] 0=amount of scratches as experienced when scratching two uncoated bottles against each other [0208] 2=amount of scratches as experienced when scratching two hot coated bottles coated with a state-of-the-art MBTC coating (coating composition 17) against each other [0209] 3=amount of scratches as experienced when scratching one hot coated bottle coated with a state-of-the-art MBTC coating (coating composition 17) and one cold coated bottle coated with a polyethylene wax coating against each other

Preparation of Coating Composition

Coating Composition 1

[0210] In a round bottom flask, BTESE (300 g, 0.846 mol; 1 eq) is dissolved in IPA (160 g). HNO3 (0.1M; 18.29 g; 0.2 eq) is added dropwise and the reaction mixture is stirred at RT for 2 h. Ti(iPropyl)+(721.35 g, 2.538 mol; 3 eq) is added dropwise over 30 min. The resulting reaction mixture is stirred at RT for 30 min. Texanol (73.20 g; 0.338 mol; 0.4 eq) and BuOH (62.71 g; 0.846 mol; 1 eq) are added. The low boiling point solvents are evaporated under vacuum (P=700 mbar; T water bath=97 C). Solvent evaporated=183.74 g.

Coating Composition 2

[0211] In a round bottom flask, MEMO (250 g, 1.007 mol; 1 eq) is dissolved in IPA (120 g). HNO3 (0.1M; 21.78 g; 0.2 eq) is added dropwise and the reaction mixture is stirred at RT for 2 h. Ti(iPropyl)+(858.32 g, 3.021 mol; 3 eq) is added dropwise over 30 min. The resulting reaction mixture is stirred at RT for 30 min. Texanol (87.13 g; 0.338 mol; 0.4 eq) and BuOH (74.63 g; 0.846 mol; 1 eq) are added. The low boiling point solvents are evaporated under vacuum (P=700 mbar; T water bath=97 C). Solvent evaporated=208.64 g.

Coating Composition 3

[0212] In a round bottom flask, n-octylTMS (500 g, 2.133 mol; 1 eq) is dissolved in IPA (140 g). HNO3 (0.1M; 23.06 g; 0.2 eq) is added dropwise and the reaction mixture is stirred at RT for 2 h. Ti(iPropyl)+(606.24 g, 2.133 mol; 3 eq) is added dropwise over 30 min. The resulting reaction mixture is stirred at RT for 30 min. A mixture of texanolacetic acid (294.75 g; 2.133 mol; 1 eq) is added. The low boiling point solvents are evaporated under vacuum (P=700 mbar; T water bath=97 C). Solvent evaporated=206.36 g.

Coating Composition 4

[0213] In a round bottom flask, MTEOS (200 g, 1.12 mol; 1 eq) is dissolved in IPA (140 g). HNO3 (0.1M; 12.08 g; 0.2 eq) is added dropwise and the reaction mixture is stirred at RT for 2 h. Ti(iPropyl)+(956.4 g, 3.37 mol; 3 eq) is added dropwise over 30 min. The resulting reaction mixture is stirred at RT for 30 min. A mixture of texanol-acetic acid (155.5 g; 1.12 mol; 1 eq) is added. The low boiling point solvents are evaporated under vacuum (P=700 mbar; T water bath=97 C). Solvent evaporated=165.21 g.

Coating Composition 5

[0214] In a round bottom flask, BTESE (125 g, 0.353 mol; 1 eq) is dissolved in IPA (50 g). HNO3 (0.1M; 7.6 g; 0.2 eq) is added dropwise and the reaction mixture is stirred at RT for 2 h. Ti(iPropyl)+(298.45 g, 1.05 mol; 3 eq) is added dropwise over 30 min. The resulting reaction mixture is stirred at RT for 30 min. Texanol (30.54 g; 0.1412 mol; 0.4 eq) and BuOH (26.16 g; 0.353 mol; 1 eq) are added. The low boiling point solvents are evaporated under vacuum (P=700 mbar; T water bath=97 C). Solvent evaporated=25.37 g.

Coating Composition 6

[0215] In a round bottom flask, MEMO (46.62 g, 0.188 mol; 1 eq) is dissolved in IPA (30 g). HNO3 (0.1M; 2.03 g; 0.2 eq) is added dropwise and the reaction mixture is stirred at RT for 2 h. Ti(iPropyl)+(160.31 g, 0.564 mol; 3 eq) is added dropwise over 30 min. The resulting reaction mixture is stirred at RT for 30 min. Texanol (8.13 g; 0.0376 mol; 0.4 eq) and BuOH (6.97 g; 0.094 mol; 1 eq) are added. The low boiling point solvents are evaporated under vacuum (P=700 mbar; T water bath=97 C). Solvent evaporated=17.01 g.

Coating Composition 7A

[0216] In a round bottom flask, n-octylTMS (65.64 g, 0.28 mol; 1 eq) is dissolved in IPA (40 g). HNO3 (0.1M; 3.04 g; 0.2 eq) is added dropwise and the reaction mixture is stirred at RT for 2 h. Ti(iPropyl)+(238.76 g, 0.84 mol; 3 eq) is added dropwise over 30 min. The resulting reaction mixture is stirred at RT for 30 min. BuOH (5.19 g; 0.07 mol; 1 eq) is added. The low boiling point solvents are evaporated under vacuum (P=700 mbar; T water bath=97 C). Solvent evaporated=206.36 g.

Coating Composition 7B

[0217] In a round bottom flask, n-octylTMS (65.64 g, 0.28 mol; 1 eq) is dissolved in IPA (40 g). HNO3 (0.1M; 3.04 g; 0.2 eq) is added dropwise and the reaction mixture is stirred at RT for 2 h. Ti(iPropyl)+(238.76 g, 0.84 mol; 3 eq) is added dropwise over 30 min. The resulting reaction mixture is stirred at RT for 30 min. Octanol (9.12 g; 0.07 mol; 1 eq) is added. The low boiling point solvents are evaporated under vacuum (P=700 mbar; T water bath=97 C). Solvent evaporated=206.36 g.

Coating Composition 7C

[0218] In a round bottom flask, n-octylTMS (65.64 g, 0.28 mol; 1 eq) is dissolved in IPA (40 g). HNO3 (0.1M; 3.04 g; 0.2 eq) is added dropwise and the reaction mixture is stirred at RT for 2 h. Ti(iPropyl)+(238.76 g, 0.84 mol; 3 eq) is added dropwise over 30 min. The resulting reaction mixture is stirred at RT for 30 min. Texanol (9.12 g; 0.07 mol; 1 eq) is added. The low boiling point solvents are evaporated under vacuum (P=700 mbar; T water bath=97 C). Solvent evaporated=206.36 g.

Coating Composition 7D

[0219] In a round bottom flask, n-octylTMS (65.64 g, 0.28 mol; 1 eq) is dissolved in IPA (40 g). HNO3 (0.1M; 3.04 g; 0.2 eq) is added dropwise and the reaction mixture is stirred at RT for 2 h. Ti(iPropyl)+(238.76 g, 0.84 mol; 3 eq) is added dropwise over 30 min. The resulting reaction mixture is stirred at RT for 30 min. A mixture of texanolacetic acid (9.67 g; 0.07 mol; 1 eq) is added. The low boiling point solvents are evaporated under vacuum (P=700 mbar; T water bath=97 C). Solvent evaporated=206.36 g.

Coating Composition 8A

[0220] In a round bottom flask, n-octylTMS (150 g, 0.64 mol; 1 eq) is dissolved in IPA (40 g). HNO3 (0.1M; 6.92 g; 0.2 eq) is added dropwise and the reaction mixture is stirred at RT for 2 h. Ti(iPropyl)+(181.9 g, 0.64 mol; 1 eq) is added dropwise over 30 min. The resulting reaction mixture is stirred at RT for 30 min. A mixture of texanol-acetic acid (29.75 g; 0.21 mol; 0.3 eq) and BuOH (15.57 g; 0.21 mol; 0.3 eq) are added. The low boiling point solvents are evaporated under vacuum (P=700 mbar; T water bath=97 C). Solvent evaporated=206.36 g.

Coating Composition 8B

[0221] In a round bottom flask, n-octylTMS (150 g, 0.64 mol; 1 eq) is dissolved in IPA (40 g). HNO3 (0.1M; 6.92 g; 0.2 eq) is added dropwise and the reaction mixture is stirred at RT for 2 h. Ti(iPropyl)+(181.9 g, 0.64 mol; 1 eq) is added dropwise over 30 min. The resulting reaction mixture is stirred at RT for 30 min. Texanol (45.4 g; 0.21 mol; 0.3 eq) and BuOH (15.57 g; 0.21 mol; 0.3 eq) are added. The low boiling point solvents are evaporated under vacuum (P=700 mbar; T water bath=97 C). Solvent evaporated=206.36 g.

Coating Composition 8C

[0222] In a round bottom flask, n-octylTMS (150 g, 0.64 mol; 1 eq) is dissolved in IPA (40 g). HNO3 (0.1M; 6.92 g; 0.2 eq) is added dropwise and the reaction mixture is stirred at RT for 2 h. Ti(iPropyl)+(181.9 g, 0.64 mol; 1 eq) is added dropwise over 30 min. The resulting reaction mixture is stirred at RT for 30 min. A mixture of texanol-acetic acid (29 g; 0.21 mol; 0.3 eq) is added. The low boiling point solvents are evaporated under vacuum (P=700 mbar; T water bath=97 C). Solvent evaporated=206.36 g.

Coating Composition 9

[0223] In a round bottom flask, MTEOS (100 g, 0.561 mol; 1 eq) is dissolved in IPA (25 g). HNO3 (0.1M; 6.07 g; 0.2 eq) is added dropwise and the reaction mixture is stirred at RT for 2 h. Ti(iPropyl)+(159.45 g, 3.37 mol; 3 eq) is added dropwise over 30 min. The resulting reaction mixture is stirred at RT for 30 min. Texanol (16.22 g; 0.075 mol; 0.4 eq) and BuOH (13.86 g; 0.187 mol; 1 eq) is added. The low boiling point solvents are evaporated under vacuum (P=700 mbar; T water bath=97 C). Solvent evaporated=27.02 g.

Coating Composition 10

[0224] In a round bottom flask, BTESE (125 g, 0.353 mol; 1 eq) is dissolved in IPA (50 g). HNO3 (0.1M; 7.6 g; 0.2 eq) is added dropwise and the reaction mixture is stirred at RT for 2 h. Ti(iPropyl)+(298.45 g, 1.05 mol; 3 eq) is added dropwise over 30 min. The resulting reaction mixture is stirred at RT for 30 min. A mixture of texanol-acetic acid (1 eq) is added. The low boiling point solvents are evaporated under vacuum (P=700 mbar; T water bath=97 C).

Coating Composition 11

[0225] In a round bottom flask, BTESE (125 g, 0.353 mol; 1 eq) is dissolved in IPA (50 g). HNO3 (0.1M; 7.6 g; 0.2 eq) is added dropwise and the reaction mixture is stirred at RT for 2 h. Ti(iPropyl)+(199 g, 0.70 mol; 2 eq) is added dropwise over 30 min. The resulting reaction mixture is stirred at RT for 30 min. Texanol (0.2 eq) is added. The low boiling point solvents are evaporated under vacuum (P=700 mbar; T water bath=97 C).

Coating Composition 12A

[0226] In a round bottom flask, Ti(iPropyl)+(3 eq) is mixed with BuOH (1 eq) and the mixture is heated to 90 C for 30 min.

Coating Composition 12B

[0227] In a round bottom flask, Ti(iPropyl)+(3 eq) is mixed with BuOH (1 eq) and the mixture is heated to 90 C for 30 min. Texanol (0.5 eq) is added.

Coating Composition 13

[0228] In a round bottom flask, n-octylTMS (1 eq) is dissolved in IPA (10 g). HNO3 (0.1M; 0.2 eq) is added dropwise and the reaction mixture is stirred at RT for 2 h. BuOH (1 eq) is added. The low boiling point solvents are evaporated under vacuum (P=700 mbar; T water bath=97 C).

Coating Composition 14

[0229] Hexyltrimethoxysilane (1 eq) is mixed in IPA (10 g). HNO3 (0.1 M; 0.2 eq) is added dropwise and the reaction mixture is stirred at RT for 2 h. BuOH (1 eq) is added and the low boing point solvents are evaporated under vacuum (P=700 mbar; T water bath=97 C).

Coating Composition 15

[0230] Zirconiumdioxide (1 eq) is mixed in IPA (10 g). HNO3 (0.1 M; 0.2 eq) is added dropwise and the reaction mixture is stirred at RT for 2 h. BuOH (1 eq) is added and the low boing point solvents are evaporated under vacuum (P=700 mbar; T water bath=97 C).

Coating Composition 16

[0231] Aluminiumoxide (Al.sub.2O.sub.3) (1 eq) is mixed in IPA (10 g). HNO3 (0.1 M; 0.2 eq) is added dropwise and the reaction mixture is stirred at RT for 2 h. BuOH (1 eq) is added and the low boing point solvents are evaporated under vacuum (P=700 mbar; T water bath=97 C).

Coating Composition 17 (MBTC)

[0232] As coating composition a state of the art coating composition comprising MBTC (monobutyltim trichloride) was used.

Coating Experiments

a) Pearlescent Effect

[0233] Coating compositions 1, 2, 3 and 4 were coated on hot glass bottles. Thereby, the colour of the coating compositions and the coating results were monitored.

[0234] The coating was applied as follows:

[0235] 200 mL of the solution of the coating composition was put in a 3 necks round bottom flask at room temperature and stirred. The reaction mixture was then heated and the temperature was measured regularly. Air was injected in the system and the vapour was pushed via an exhaust line to a bottle (heated at very high temperatures, about) 600? C. to be coated.

[0236] After procedure, the coated jar was placed into annealing oven at T=210? C. for 30 min.

[0237] The observations about monitored colour, vapour formation and sample coating are listed in Tables 1?4 for coating compositions 1?4

TABLE-US-00001 TABLE 1 monitored colour, vapour formation and sample coating of coating composition 1 Temper- Boil- Time ature Solution ing [min] [? C.] colour Y/N Comments/Sample Coating 5 65 Champagne N 10 84 Champagne N Lots of bubbles 11 89 Champagne Y A bit of foam 12 91 Champagne Y Poor vapour formation 19 103 Champagne Y Poor vapour formation 21 107 Champagne Y Poor vapour formation; 1.sup.st bottle: no pearlescent effect 23 115 Champagne Y About to stop boiling 24 120 Champagne Y/N Good vapour formation with air injection 26 123 Champagne N 31 146 Champagne N 2.sup.nd bottle: no pearlescent effect 36 160 Bit darker N Good vapour formation with air injection 41 181 Bit darker N 3.sup.rd bottle: very light pearlescent effect 44 185 Olive oil N 50 199 Amber N 51 200 Amber N 4.sup.th bottle: light pearlescent effect 53 204 Cognac N Solution gets darker quickly 55 207 Tea N 61 217 Light coffee N 5.sup.th bottle: pearlescent effect 62 202 Coffee N 6.sup.th bottle: 2 coating rounds, pearlescent effect 64 212 Dark coffee N

TABLE-US-00002 TABLE 2 monitored colour, vapour formation and sample coating of coating composition 2 Temper- Boil- Time ature Solution ing [min] [? C.] colour Y/N Comments/Sample Coating 10 84 Champagne N 11 85.5 Champagne Y 15 90 Champagne Y poor vapour formation; 1.sup.st bottle: no pearlescent effect 25 105 Champagne Y/N poor vapour formation; 2.sup.nd bottle: no pearlescent effect 28 115 Champagne N 30 124 Champagne Y/N 32 127 Champagne N 35 137 Champagne N good vapour formation; 3.sup.rd bottle: pearlescent effect 38 141 Champagne N 42 150 Champagne N 45 158 Champagne N 4.sup.th bottle: light pearlescent effect 50 169 Olive oil N 55 184 Amber N 5.sup.th bottle: pearlescent effect 57 184 Cognac N 63 193 Tea N 65 195 Coffee N 6.sup.th bottle: pearlescent effect 70 198 Dark coffee N 72 199.5 Black N 75 204 Black N 7.sup.th bottle: pearlescent effect 77 202 black N 8.sup.th bottle: 2 coating rounds, strong pearlescent effect

TABLE-US-00003 TABLE 3 monitored colour, vapour formation and sample coating of coating composition 3 Temper- Boil- Time ature Solution ing [min] [? C.] colour Y/N Comments/Sample Coating 8 66 Champagne N 13 86 Champagne Y Starts boiling, some foam, no vapour without air injection 23 98 Champagne Y no vapour without air injection 32 120 Champagne Y some vapour without air injection 34 125 Champagne Y About to stop boiling, poor vapour formation 36 130 Champagne Y poor vapour formation; 1.sup.st bottle: no pearlescent effect 38 138 Champagne Y Vapour formation without air injection 46 147 Champagne Y poor vapour formation; 2.sup.nd bottle: no pearlescent effect 48 150 Champagne N Stop boiling 52 161 Olive oil N 56 175 Olive oil N good vapour formation; 3.sup.rd bottle: no pearlescent effect 60 180 Amber N good vapour formation 63 186 Cognac N Very good vapour formation 65 190 Tea N 66 195 Dark tea N good vapour formation; 4.sup.th bottle: no pearlescent effect 68 196 Light N coffee 72 198 Coffee N 74 202 Coffee N Massive vapour formation; 5.sup.th bottle: light pearlescent effect 76 195 Dark coffee N 6.sup.th bottle: 2 coating rounds, pearlescent effect

TABLE-US-00004 TABLE 4 monitored colour, vapour formation and sample coating of coating composition 4 Temper- Boil- Time ature Solution ing [min] [? C.] colour Y/N Comments/Sample Coating 11 82 Champagne N 12 87 Champagne Y Starts boiling 20 107 Champagne Y 1.sup.st bottle: not enough vapour for coating 22 114 Champagne Y good vapour with air injection 30 140 Champagne N 2.sup.nd bottle; not enough vapour for coating 38 170 Champagne Y Starts boiling again 40 175 Champagne Y good vapour formation; 3.sup.rd bottle: no pearlescent effect 42 178 Champagne N 48 197 Champagne Y Some boiling 50 201 Bit Y good vapour formation; yellowing 4.sup.th bottle: no pearlescent effect 52 202 Olive oil N 54 208 Galliano Y Some boiling 56 212 Amber Y Good boiling 60 214 Cognac Y Massive vapour formation; 5.sup.th bottle: light pearlescent effect 62 215 Tea N Some boiling 64 218 Tea Y 66 220 Dark tea Y 68 220 Light Y coffee 70 221 Light Y Massive vapour formation; coffee 7.sup.th bottle: light pearlescent effect 76 223.4 Coffee Y 80 223.4 Dark coffee Y Massive vapour formation; 7.sup.th bottle: pearlescent effect 81 200 Dark coffee Y 8.sup.th bottle: 2 coating rounds, pearlescent effect

[0238] The coated bottles were subjected to a slipping and scratch resistance tests. A summary of the slipping and scratch resistance tests is shown in Table 5:

TABLE-US-00005 TABLE 5 Summary of the Slipping tests Composition 1 Composition 2 Composition 3 Composition 4 Slipping Scratch Slipping Scratch Slipping Scratch Slipping Scratch Bottles 1-2 1.5 1 4 1 1.5 1 0 1 Bottles 2-3 3 1 5 1 1 1 0 1 Bottles 3-4 3.5 1 5 2.5 1.5 1 0 1 Bottles 4-5 3.5 1 5 2.5 2 1 0 1 Bottles 5-6 1.5 1 4 2 2 1 0 1 Bottles 6-7 1.5 1 0 1 Bottles 7-8 3 1 0 2

b) Mechanical Properties

[0239] In a first coating experiment coating compositions 5, 7A, 8A, 8C, 10, 11, 12A, 12B, 13, 14, 15 and 16 were coated on hot glass jars.

[0240] The coating was applied as follows:

[0241] A glass jar was heated in an IR furnace at a temperature of 600? C. for 30 min and was then directly put on a circulating turntable.

[0242] In the meantime the solution of the coating composition was put in a 3 necks round bottom flask at room temperature and stirred. The solution of the coating composition was heated until vapour formation was clearly detectable. Air was injected in the system and the vapour was pushed via an exhaust line to the outer surface of the heated glass jar (about 600? C.).

[0243] In a first set of coating the jars were coated in two rounds of coating at an overall time of 30 seconds on a turntable.

[0244] In a second set of coating the jars were coated in one round of coating at an overall time of 15 seconds on a turntable.

[0245] In a third set of coating, the coating thickness (estimated 50-100 nm) was standardized by regulating air pressure and adjusting the smoke output nozzle close to the jar surface (10 nm).

[0246] After procedure, the coated jar was placed into annealing oven at T=210? C. for 30 min.

[0247] The coated jars were visually inspected and subjected to a slipping and scratch resistance test. A summary of the slipping and scratch resistance tests of the first set of coating is shown in Table 6. A summary of the slipping and scratch resistance tests of the second set of coating is shown in Table 7.

TABLE-US-00006 TABLE 6 Summary of the visual inspection and the slipping and scratch resistance tests of the first set of coating Coating Solution composition Visual Slipping Scratch Sum appearance 5 2 4 2 8 yellowish 10 2 4 2.5 8.5 yellowish 11 1.5 4 2.5 8 yellow 7C 1.5 2 2 5.5 Slightly yellowish 12A 1 3 2 6 Slightly yellowish 12B 1 3.5 2 6.5 Slightly yellowish 14 3 1 1 5 15 3 1 1 5 16 3 1.5 1 5.5

TABLE-US-00007 TABLE 7 Summary of the visual inspection and the slipping and scratch resistance tests of the first set of coating Coating Solution composition Visual Slipping Scratch Sum appearance 5 2 4 2.5 8.53 yellowish 13 3 1 1 5 Clear solution 8A 3 2 1.5 6.5 yellow 8C 3 3.5 2.5 9 yellowish

[0248] In a second coating experiment coating compositions 5 and 17 were coated on hot glass bottles.

[0249] The coating was applied as follows:

[0250] A glass bottle was heated in two steps firstly for 1 h at 210? C. and afterwards in an IR furnace at a temperature of 600? C. for 30 min and was then directly put on a circulating turntable.

[0251] In the meantime the solution of the coating composition was put in a 3 necks round bottom flask at room temperature and stirred. The solution of the coating composition was heated until vapour formation was clearly detectable. Air was injected in the system and the vapour was pushed via an exhaust line to the outer surface of the heated glass jar (about 600? C.).

[0252] The bottles were coated in one round of coating at an overall time of 15 seconds on a turntable.

[0253] Coating thickness was standardized to an estimated thickness of about 50 to 100 nm by regulating air pressure and adjusting the vapour output nozzle close to the bottle surface (about 10 mm).

[0254] After the coating procedure the coated bottle was placed into an annealing oven at 210? C. for 30 min for annealing.

[0255] The coated bottles were visually inspected and subjected to a slipping and scratch resistance test. A summary of the slipping and scratch resistance tests is shown in Table 8.

TABLE-US-00008 TABLE 8 Summary of the visual inspection and the slipping and scratch resistance tests Coating compo- Solution Other sition Visual Slipping Scratch Sum appearance observations 5 2 4.5 2.5 9 Clearish Strong (slightly vapour iridescent formation of too thick 17 2 3 2 7 clear Only light vapour formation