阅读说明：本技术 涂覆的基材和制备方法 (Coated substrate and method of making ) 是由 J·布朗 C·梅丁 D·雷兹贝克 K·S·瓦尔马 于 2020-03-27 设计创作，主要内容包括：涂覆的玻璃基材,包含透明玻璃基材,其涂覆有包含具有Si-O-Si键的材料和阻挡组分的阻挡层,其中阻挡组分包含荧光酮和/或荧光酮衍生物。(A coated glass substrate comprising a transparent glass substrate coated with a barrier layer comprising a material having Si-O-Si bonds and a barrier component, wherein the barrier component comprises a fluorone and/or a fluorone derivative.)

1. A coated glass substrate comprising:

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

2. The coated glass substrate of claim 1, wherein the transparent glass substrate is a glass container and the barrier layer is located on an outer surface of the container.

3. The coated glass substrate of any of the preceding claims, wherein the material having Si-O-Si bonds comprises a material having a cross-linked network of Si-O-Si bonds, preferably wherein the material having Si-O-Si bonds further comprises one or more organic functional groups.

4. The coated glass substrate of any of the preceding claims, wherein the barrier layer further comprises a polyol and/or a diol.

5. The coated glass substrate of any of the preceding claims, wherein the fluorone derivative comprises calcein, carboxyfluorescein diacetate succinimidyl ester, carboxyfluorescein succinimidyl ester, 6-carboxyfluorescein, dichlorofluorescein, eosin B, eosin Y, erythrosine, fluo-3, fluo-4, fluorescein imide, fluorescein isothiocyanate, indoxanthin, mercurobromide red, 3-carboxy-6, 8-difluoro-7-hydroxycoumarin (pacific blue), phloxine, rhodamine B, rhodamine 6G, rhodamine 123, carboxytetramethylrhodamine (TAMRA), tetramethylrhodamine (mrtmr), and isothiocyanate derivatives thereof (TRITC), sulforhodamine 101 (and its sulfonyl chloride form, texas red), and its sulfonyl chloride form, One or more of rhodamine red, NHS-rhodamine and heminaphthol rhodamine fluorescence.

6. The coated glass substrate of any of the preceding claims, wherein the fluorone and/or fluorone derivative comprises rhodamine and/or rhodamine derivative.

7. The coated glass substrate according to any of the preceding claims, wherein the coated glass substrate comprises a transparent glass substrate coated with a barrier layer comprising a material having Si-O-Si bonds and a barrier component,

wherein the barrier component comprises a fluorone and/or a fluorone derivative,

wherein the transparent glass substrate is a glass container,

wherein the barrier layer coats at least 80% of the outer surface of the container,

wherein the material having Si-O-Si bonds comprises a material having a cross-linked network of Si-O-Si bonds,

wherein the blocking component is a material capable of blocking electromagnetic radiation in the wavelength range of 350-500nm, and

wherein the fluorone and/or fluorone derivative comprises rhodamine and/or a rhodamine derivative.

8. The method of making a coated glass substrate according to any of the preceding claims, the method comprising the steps of:

a) preparing a solution or mixture by mixing at least the following components: a silane, a barrier component, water, and an acid, wherein the barrier component comprises a fluorone and/or a fluorone derivative;

b) applying the solution or mixture to a surface of a transparent glass substrate; and

c) curing the applied solution or mixture.

9. The process according to claim 8, wherein in step a) the solution or mixture is aged for at least 2 hours, more preferably at least 7 hours, even more preferably at least 10 hours, most preferably at least 12 hours after mixing.

10. The method according to claim 8 or 9, wherein in step b) the temperature of the transparent glass substrate is below 150 ℃, preferably below 100 ℃, more preferably below 70 ℃, most preferably below 50 ℃ when the solution or mixture is applied to the surface of the transparent glass substrate.

11. The method according to any one of claims 8 to 10, wherein in step c) the applied solution or mixture is cured for at least 20 minutes, preferably at least 40 minutes, more preferably at least 50 minutes, most preferably at least 55 minutes, but preferably at most 24 hours, more preferably at most 10 hours, even more preferably at most 3 hours, most preferably at most 1.5 hours.

12. The method according to any one of claims 8 to 11, wherein in step c) the applied solution or mixture is cured at a temperature above 20 ℃, preferably above 100 ℃, more preferably above 160 ℃, most preferably above 190 ℃, but preferably below 400 ℃, more preferably below 300 ℃, even more preferably below 240 ℃, most preferably below 210 ℃.

13. The method of any one of claims 8 to 12, wherein the silane is represented by formula (1):

SiX₄ (1)

wherein X is a hydrolyzable functional group or a halogen atom.

14. The method according to any one of claims 8 to 13, wherein the silane is a tetraalkoxysilane, such as Tetraethoxysilane (TEOS).

15. The method of any one of claims 8 to 14, wherein the components mixed in step a) further comprise a silane coupling agent represented by formula (2):

R¹ _mR² _nSiX_4-m-n (2)

wherein R is¹Being an organic radical having a reactive functional group, R²Is an organic group having no reactive functional group, X is a hydrolyzable 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.

16. The method of claim 15, 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.

17. The process according to any one of claims 8 to 16, wherein the solution or mixture prepared in step a) has a molar percentage (mol%) of polyols and/or diols 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%.

18. The process according to any one of claims 8 to 17, wherein in step a), the solution or mixture is aged for at least 2 hours after mixing;

wherein in step b), the temperature of the transparent glass substrate is less than 50 ℃ when the solution or mixture is applied to the surface of the transparent glass substrate;

wherein the silane is a tetraalkoxysilane;

wherein the components mixed in step a) further comprise a silane coupling agent represented by formula (2):

R¹ _mR² _nSiX_4-m-n (2)

wherein R is¹Being an organic radical having a reactive functional group, R²Is an organic group having no reactive functional group, X is a hydrolyzable 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 is

Wherein the fluorone and/or fluorone derivative comprises rhodamine and/or a rhodamine derivative.

19. Use of fluorone and/or fluorone derivative as UV blocking component of a barrier layer coating a transparent glass substrate, wherein said barrier layer further comprises a material having Si-O-Si bonds.

20. Use of a fluorone and/or fluorone derivative for improving the moisture resistance of a barrier layer coating a transparent glass substrate, wherein said barrier layer further comprises a material having a Si-O-Si bond.

Examples

Uvinul ^TM3050 from Sigma-Aldrich ^TM. Rhodamine 6G from Sigma-Aldrich^TM。BYK ^TM345 from BYK^TM. GPTMS from Sigma-Aldrich^TM. TEOS obtained from Sigma-Aldrich^TM。

Comparative example 1

The solution/mixture was prepared by stirring the components shown in table 1 below for 35 minutes.

Table 1: the masses of the components of the solution/mixture prepared in comparative example 1 are shown

After stirring, the solution/mixture was allowed to stand at 5 ℃ for 12 hours for aging. The solution/mixture was then sprayed onto clear, colorless flint bottles at a temperature of 20 ℃. Spray coating was performed using two nozzles, a PTFE tube and a syringe driver. The applied solution/mixture was then cured at 200 ℃ for 2 hours

Using PerkinElmer^TMThe Lambda 900 spectrometer tests the light transmission characteristics of the resulting coated shoulder. The results are shown in fig. 1 and discussed below.

Example 1

Solutions/mixtures were prepared using the components shown in table 2 below and the same method as comparative example 1.

Table 2: the masses of the components used in the solution/mixture prepared in example 1 are shown

After stirring, the solution/mixture was allowed to stand at 5 ℃ for 12 hours for aging. The clear, colorless flint bottle was then sprayed with the solution/mixture at a temperature of 120 c using the same method as in comparative example 1. The applied solution/mixture was then cured at 200 ℃ for 2 hours.

Another clear, colorless flint bottle was coated in the same manner as the previous section using the same solution/mixture prepared with the components shown in table 2, except that a thicker coating was deposited.

Both coated bottles of example 1 exhibited a striking pink color, with the thicker coating layer being more intense in color than the thinner coating layer.

The resulting coated bottles were tested for light transmission characteristics as in comparative example 1. Uncoated, clear, colorless flint bottles were also tested in the same manner. The results are shown in fig. 1 and discussed below.

Results

UV blocking capability

FIG. 1 shows an uncoated, clear, colorless flint bottle (labeled uncoated), a coated bottle prepared as in comparative example 1 (Uvinul)^TM3050) And a plot of percent transmission versus wavelength for the thin and thick coated bottles prepared in example 1 (rhodamine 6G thin coating and rhodamine 6G thick coating, respectively).

It will be noted that both the bottle of comparative example 1 and the two bottles of example 1 exhibit UV blocking capability compared to the uncoated colorless bottle. Indeed, in the wavelength range of 380-500nm, which is of particular interest for beer skunks, the bottle of example 1 performs better than the bottle of comparative example 1. The decrease in transmission from thin to thick coatings in example 1 demonstrates how the UV blocking properties can be fine tuned together with the color intensity.

Moisture resistance

Two clear (flint) bottles were coated: one according to comparative example 1 and one according to example 1. Samples having dimensions of about 4cm by 3cm and a thickness equal to the bottle thickness were cut from the body of each bottle.

These samples were evaluated by humidity testing to investigate their resistance to harsh environments. The machine used is Thermotron^TM7800 Environmental Chamber and conditions 95% humidity and 50 ℃. Examination after 24 hours and after 48 hoursAnd (3) sampling.

After 24 hours:

sample of comparative example 1: delamination of the coating occurs. The speckled coating remained on the sample.

Sample of example 1: the coating was visually free of visible defects and also showed no signs of delamination.

After 48 hours:

sample of comparative example 1: the coating delaminates further and the coverage of the coating is even lower.

Sample of example 1: the coating was visually free of visible defects and also showed no signs of delamination.

These results clearly demonstrate the improved moisture resistance of the coated glass substrates of the present invention.

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.