COATED SUBSTRATE AND PROCESS OF PREPARATION

Abstract

A coated glass substrate comprising: a transparent glass substrate coated with a blocking layer comprising a material having Si—O—Si bonds and a blocking component, wherein the blocking component comprises fluorone and/or a fluorone derivative.

Claims

1.-20. (canceled)

21. A coated glass substrate comprising: a transparent glass substrate coated with a blocking layer comprising a material having Si—O—Si bonds and a blocking component, wherein the blocking component comprises fluorone and/or a fluorone derivative.

22. The coated glass substrate according to claim 21, wherein the transparent glass substrate is a glass container and wherein the blocking layer is located on the external surface of the container.

23. The coated glass substrate according to claim 21, wherein the material having Si—O—Si bonds comprises a material having a crosslinked network of Si—O—Si bonds, preferably wherein the material having Si—O—Si bonds further comprises one or more organic functional groups.

24. The coated glass substrate according to claim 21, wherein the blocking layer further comprises a polyol and/or diol.

25. The coated glass substrate according to claim 21, wherein the fluorone derivative comprises one or more of calcein, carboxyfluorescein diacetate succinimidyl ester, carboxyfluorescein succinimidyl ester, 6-carboxyfluorescein, dichlorofluorescein, eosin, eosin B, eosin Y, erythrosine, fluo-3, fluo-4, fluorescein, fluorescein amidite, fluorescein isothiocyanate, Indian yellow, merbromin, 3-carboxy-6,8-difluoro-7-hydroxycoumarin (Pacific blue), phloxine, rhodamine, rhodamine B, rhodamine 6G, rhodamine 123, carboxytetramethylrhodamine (TAMRA), tetramethylrhodamine (TMR) and its isothiocyanate derivative (TRITC), sulforhodamine 101 (and its sulfonyl chloride form Texas red), rhodamine red, NHS-rhodamine and seminaphtharhodafluor.

26. The coated glass substrate according to claim 21, wherein the fluorone and/or a fluorone derivative comprises rhodamine and/or a rhodamine derivative.

27. The coated glass substrate according to claim 21, wherein the coated glass substrate comprises: a transparent glass substrate coated with a blocking layer comprising a material having Si—O—Si bonds and a blocking component, wherein the blocking component comprises fluorone and/or a fluorone derivative, wherein the transparent glass substrate is a glass container, wherein the blocking layer coats at least 80% of the external surface of the container, wherein the material having Si—O—Si bonds comprises a material having a crosslinked network of Si—O—Si bonds, wherein the blocking component is a material that is capable of blocking electromagnetic radiation in the wavelength range 350-500 nm, and wherein the fluorone and/or a fluorone derivative comprises rhodamine and/or a rhodamine derivative.

28. A process for preparing a coated glass substrate in accordance with claim 21, said process comprising the following steps: a) preparing a solution or mixture by mixing at least the following components: a silane, a blocking component, water and an acid, wherein the blocking component comprises fluorone and/or a fluorone derivative; b) applying said solution or mixture to a surface of a transparent glass substrate; and c) curing the applied solution or mixture.

29. The process according to claim 28, wherein, in step a) following the mixing the solution or mixture is aged for at least 2 hr, more preferably at least 7 hr, even more preferably at least 10 hr, most preferably at least 12 hr.

30. The process according to claim 28, wherein, in step b), when the solution or mixture is applied to the surface of the transparent glass substrate, said transparent glass substrate is at a temperature of less than 150° C., preferably less than 100° C., more preferably less than 70° C., most preferably less than 50° C.

31. The process according to claim 28, wherein, in step c), the applied solution or mixture is cured for at least 20 min, preferably at least 40 min, more preferably at least 50 min, most preferably at least 55 min, but preferably at most 24 hr, more preferably at most 10 hr, even more preferably at most 3 hr, most preferably at most 1.5 hr.

32. The process according to claim 28, wherein, in step c), the applied solution or mixture is cured at a temperature of greater than 20° C., preferably greater than 100° C., more preferably greater than 160° C., most preferably greater than 190° C., but preferably less than 400° C., more preferably less than 3000° C., even more preferably less than 240° C., most preferably less than 210° C.

33. The process according to claim 28, wherein the silane is represented by the formula (1):
SIX.sub.4(1) wherein X is a hydrolysable functional group or a halogen atom.

34. The process according to claim 28, wherein the silane is a tetraalkoxysilane such as tetraethoxysilane (TEOS).

35. The process according to claim 28, wherein the components mixed in step a) further comprise a silane coupling agent represented by the formula (2):
R.sup.1.sub.mR.sup.2.sub.nSiX.sub.4-m-n  (2) wherein R.sup.1 is an organic group having a reactive functional group, R.sup.2 is an organic group having no reactive functional group, X is a hydrolysable functional group or a halogen atom, m is an integer of 1 to 3, n is an integer of 0 to 2, and m+n is an integer of 1 to 3.

36. The process according to claim 35, wherein the silane coupling agent comprises one or more of vinyltriethoxysilane, p-styryltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane (GPTMS), 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and derivatives.

37. The process according to claim 28, wherein the solution or mixture prepared in step a) has a molar percentage (mol %) of the polyol and/or diol of at least 2 mol %, preferably at least 4 mol %, more preferably at least 5 mol %, most preferably at least 6 mol %, but preferably at most 20 mol %, more preferably at most 15 mol %, even more preferably at most 10 mol %, most preferably at most 7 mol %.

38. The process according to claim 28, wherein in step a) following the mixing the solution or mixture is aged for at least 2 hr; wherein in step b), when the solution or mixture is applied to the surface of the transparent glass substrate, said transparent glass substrate is at a temperature of less than 50° C.; wherein the silane is a tetraalkoxysilane; wherein the components mixed in step a) further comprise a silane coupling agent represented by the formula (2):
R.sup.1.sub.mR.sup.2.sub.nSiX.sub.4-m-n  (2) wherein R.sup.1 is an organic group having a reactive functional group, R.sup.2 is an organic group having no reactive functional group, X is a hydrolysable functional group or a halogen atom, m is an integer of 1 to 3, n is an integer of 0 to 2, and m+n is an integer of 1 to 3; and wherein the fluorone and/or a fluorone derivative comprises rhodamine and/or a rhodamine derivative.

39. A method of forming a coated transparent glass substrate comprising depositing a blocking layer coating over the substrate, wherein fluorine and/or fluorine derivative is utilized as a UV blocking component of the blocking layer coating and the blocking layer coating further comprises a material having Si—O—Si bonds.

Description

[0103] FIG. 1 is a graph of percentage transmission vs wavelength for an uncoated colourless bottle, a coated bottle outside the scope of the present invention and two coated bottles according to the present invention with different coating thicknesses.

EXAMPLES

[0104] Uvinul™ 3050 was obtained from Sigma-Aldrich™. Rhodamine 6G was obtained from Sigma-Aldrich™. BYK™-345 was obtained from BYK™. The GPTMS was obtained from Sigma-Aldrich. The TEOS was obtained from Sigma-Aldrich.

Comparative Example 1

[0105] A solution/mixture was prepared by stirring the components shown below in Table 1 for 35 min.

TABLE-US-00001 TABLE 1 showing the mass of each component used for the solution/ mixture prepared in Comparative Example 1 BYK ™-345 Conc. HNO.sub.3 Uvinul ™ Ethanol (5% Ethanol) GPTMS TEOS (5% Ethanol) Water 3050 (g) (g) (g) (g) (g) (g) (g) 2.5 28.9 0.8 11.3 22.6 0.5 33.4

[0106] Following stirring, the solution/mixture was aged by allowing it to stand for 12 hr at 5° C. A clear, colourless, flint bottle at a temperature of 20° C. was then spray coated with the solution/mixture. The spray coating was carried out using two nozzles, PTFE tubing and syringe drivers. The applied solution/mixture was then cured at 200° C. for 2 hr.

[0107] The light transmission characteristics of the shoulder of the resultant coated bottle were tested using a PerkinElmer™ Lambda 900 spectrometer. The results are shown in FIG. 1 and discussed below.

Example 1

[0108] A solution/mixture was prepared using the components shown below in Table 2 and the same approach as Comparative Example 1.

TABLE-US-00002 TABLE 2 showing the mass of each component used for the solution/ mixture prepared in Example 1 BYK ™-345 Conc. HNO.sub.3 Rhodamine Ethanol (5% GPTMS TEOS (5% Water 6G (g) (g) Ethanol) (g) (g) (g) Ethanol) (g) (g) 1.0 28.9 0.8 11.3 22.6 0.5 34.9

[0109] Following stirring, the solution/mixture was aged by allowing it to stand for 12 hr at 5° C. A clear, colourless flint bottle at a temperature of 120° C. was then spray coated with the solution/mixture using the same approach as Comparative Example 1. The applied solution/mixture was then cured at 200° C. for 2 hr.

[0110] The same solution/mixture prepared using the components shown in Table 2 was utilised in the same manner as in the preceding paragraph to coat another clear, colourless flint bottle except that a thicker coating was deposited.

[0111] Both of the coated bottles of Example 1 exhibited a conspicuous pink colouration, with the colour of the thicker coating being a more intense pink than that of the thinner coating.

[0112] The light transmission characteristics of the resultant coated bottles were tested as in Comparative Example 1. An uncoated, clear, colourless flint bottle was also tested in the same manner. The results are shown in FIG. 1 and discussed below.

[0113] Results

[0114] UV Blocking Capability

[0115] FIG. 1 shows a graph of percentage transmission vs wavelength for an uncoated, clear, colourless flint bottle (labelled Uncoated), the coated bottle prepared in Comparative Example 1 (Uvinul™ 3050) and the thin and thick coated bottles prepared in Example 1 (Rhodamine 6G, thin coating and Rhodamine 6G, thick coating respectively).

[0116] As will be noted, the bottle of Comparative Example 1 and both the bottles of Example 1 exhibited UV blocking capability in comparison with the uncoated colourless bottle. Indeed, the bottles of Example 1 performed better than the bottle of Comparative Example 1 in the wavelength range of 380-500 nm which is of particular interest for the skunking of beer. The reduction in transmission from the thin coating to the thick coating of Example 1 demonstrates how the UV blocking performance can be fine-tuned alongside the intensity of the colour.

[0117] Durability to Humidity

[0118] Two clear (flint) bottles were coated: one according to Comparative Example 1 and one according to Example 1. A sample with dimensions of approximately 4 cm×3 cm and a thickness the same as the thickness of the bottle was cut from the body of each bottle.

[0119] These samples were assessed via humidity testing to investigate their resistance to harsh environments. The machine used was a Thermotron™ 7800 Environmental Chamber and the conditions were 95% humidity and 50° C. The samples were checked after 24 hours and after 48 hours.

[0120] After 24 Hours:

[0121] Comparative Example 1 Sample—coating delamination had occurred. Patchy coating remaining on sample.

[0122] Example 1 Sample—coating had no clear defects visually, and no signs of delamination.

[0123] After 48 hours:

[0124] Comparative Example 1 Sample—further delamination of coating with even less coverage of coating apparent.

[0125] Example 1 Sample—coating had no clear defects visually, and no signs of delamination.

[0126] These results clearly demonstrate the improved durability to humidity of the coated glass substrates of the present invention.

[0127] The invention is not restricted to the details of the foregoing embodiments. The invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.