Method for treating glass surfaces

Abstract

The present invention relates to a method for treating glass surfaces, to a substrate comprising a glass surface treated by the method of the invention, and to the use of said substrate.

Description

[Technical Field]

[0001] The present invention relates to a method for treating at least one glass surface, preferably the surface of a glass container such as a glass bottle, a substrate treated with the method according to the invention and uses thereof.

[0002] Background technology Glass derives its strength and optical properties from a flawless surface, and surface damage, such as scratches or cracks present on its surface, significantly reduces its (basic) strength, especially its compressive strength. Furthermore, the internal bursting strength (also called internal pressure resistance) of glass containers, such as bottles, can be weakened by surface damage. Such bottles may burst, posing a serious risk to anyone using such damaged bottles, especially when they contain carbonated beverages. Such scratches and cracks are often caused by normal handling of glass, e.g., glass bottles containing beverages, during use or shipping. Surface damage to glass also results in optical defects, especially when used for decorative purposes, where a clear and smooth glass surface is usually desired. Examples of products where surface damage is typically unacceptable to consumers are mirrors, window panes, and decorative glassware.

[0003] Glass is often surface-treated to prevent scratches and loss of strength. This surface treatment protects the glass surface from surface damage. Typically, tin salts are applied to the glass surface at a temperature of approximately 500°C to form a thin tin oxide layer. A subsequent layer containing a gliding agent (also known in the art as a lubricant), such as wax, is then formed at a much lower temperature to reduce the glass surface's vulnerability to scratches from handling. Tin oxide is necessary to provide sufficient adhesion of the gliding agent to the glass surface. Tin salts are often ecologically problematic and harmful to humans. Therefore, organotin compounds are under regulatory pressure, and monobutyltin trichloride, one of the tin compounds most frequently used to coat glass bottles, is being phased out in Europe for this use (ECHA CoRAP list). However, despite various alternatives being explored without achieving the same protective properties, tin compounds remain in use due to the lack of available acceptable alternatives.

[0004] Various silanes and siloxanes have been proposed as replacements for tin salts. These systems primarily use epoxy and amino-functional silanes and siloxanes.

[0005] Australian Patent No. 715826 (Australian Application No. 199731796) teaches the use of lubricants such as monoaminosilanes and polyolefins on glass products to impart a degree of abrasion resistance to the surface.

[0006] US Patent No. 6,096,394 discloses the use of organopolysiloxanes in cold end coatings for glassware.

[0007] JP 2004-196563 A describes the application of a formulation containing a silane and a polymer dispersion. The silane is a monosilylsilane or (triethoxysilylproply)tetrasulfide. In the latter case, the odor of the sulfur silane is unacceptable for application to glass bottles, especially those containing beverages.

[0008] However, to date, prior art coatings using silanes or compounds derived therefrom lack scratch resistance (i.e., dry and wet scratch resistance), especially wet scratch resistance. Furthermore, many silane-based systems suffer from poor stability of the treatment solutions containing these compounds, requiring frequent replacement of such treatment solutions, which is environmentally and economically undesirable. Due to these shortcomings, silane-based systems have not been introduced into industry, especially for large-scale applications.

[0009] Object of the invention It is therefore an object of the present invention to overcome the drawbacks of the prior art.A further object of the present invention is to provide a method which allows for a sufficiently high scratch resistance of the treated glass surface without the use of ecologically harmful tin compounds.

[0010] It is of further concern that the optical appearance of the treated glass is not impaired by either the treatment itself or by damage caused by conventional handling. Additionally, the adhesion of labels attached to the treated glass surface must be acceptable.

[0011] Summary of the Invention These objects are provided by a method for treating at least one glass surface according to the invention, comprising: a) providing a substrate comprising at least one glass surface; b) treating at least one glass surface with a compound of formula (A) [ka] During the ceremony, Each R a1 are independently selected from the group consisting of hydrogen, alkyl groups, polyether groups, and aryl groups; Each R a2 are independently an alkanediyl group, R a3 is selected from the group consisting of hydrogen, alkyl groups, and aryl groups; m is an integer ranging from 0 to 3; n is an integer ranging from 0 to 3 with a silane formulation comprising at least one bis-silyl compound comprising at least one building block according to c) treating at least one glass surface with an additional formulation comprising at least one lubricant selected from the group consisting of waxes, fatty acids and fatty acid esters, so as to obtain at least one treated glass surface. The problem is solved by a method including:

[0012] Advantageously, the silane formulations used in the method according to the invention are extremely stable and can be used and stored for a sufficiently long period of time. Since tin compounds are no longer required, the invention is ecologically friendly.

[0013] The method according to the invention can advantageously reduce the number of scratches on at least one glass surface, thereby reducing the loss of (basic) strength and internal pressure resistance of the substrate, in particular of hollow containers such as bottles, during use and handling.

[0014] The following description and the dependent claims set out preferred embodiments which particularly well solve the above objects.

[0015] Detailed Description of the Invention Throughout this specification, percentages are weight percentages (wt%) unless otherwise specified. Yields are given as a percentage of the theoretical yield. Concentrations given herein refer to the mass of the total solution or dispersion unless otherwise specified.

[0016] The term "alkyl" according to the present invention includes branched or unbranched alkyl groups containing cyclic and / or acyclic structural elements, the cyclic structural elements of which of course require at least 3 carbon atoms. C1-CX-alkyl in the present specification and claims refers to alkyl groups having 1 to X carbon atoms, where X is an integer. C1-C18-alkyl includes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, tert-pentyl, neo-pentyl, hexyl, heptyl and octyl, hexadecyl and octadecyl, among others. Alkyl groups are typically unsubstituted unless otherwise specified below.

[0017] The term "alkanediyl" refers to the corresponding group having two free valencies (bonding sites). Alkanediyl is sometimes referred to in the art as "alkylene". The residue according to the present invention may contain cyclic and / or acyclic structural elements and may be linear and / or branched. C1-C4-alkanediyl includes, for example, methane-1,1-diyl, ethane-1,2-diyl, ethane-1,1-diyl, propane-1,3-diyl, propane-1,2-diyl, propane-1,1-diyl, butane-1,4-diyl, butane-1,3-diyl, butane-1,2-diyl, butane-1,1-diyl, butane-2,3-diyl, among others. Usually, alkanediyl groups are unsubstituted unless otherwise specified below.

[0018] "Alkenyl" is an unsaturated alkyl group containing at least one olefinic (i.e., C=C-double) bond. The above details and preferences for alkyl groups apply mutatis mutandis to alkenyl groups.

[0019] The term "aryl" according to the present invention refers to an aromatic hydrocarbon residue in cyclic form, such as phenyl or naphthyl. Aryl groups are typically unsubstituted unless otherwise specified below.

[0020] The term "alkaryl" according to the present invention refers to a hydrocarbon group containing at least one aryl and at least one alkyl group, such as benzyl and p-tolyl. Attachment of such an alkaryl group to another moiety can occur through the alkyl or aryl group of the alkaryl group. The above details and preferences for alkyl and aryl groups apply mutatis mutandis to the alkaryl group.

[0021] When two or more residues (which may be atoms, groups of atoms, or entire building blocks) are selected from a given group, unless otherwise specified below, it is meant that each of the residues is selected independently of the other, and that they may be selected to be the same or different members of said group. Bonding sites in some chemical formulas herein are indicated by wavy lines, as is conventional in the art. [ka] can be emphasized by

[0022] The embodiments and preferences described for one aspect of the invention apply mutatis mutandis to all other aspects unless technically feasible or otherwise stated, and repetition has been omitted to improve the brevity of this specification.

[0023] The method of the present invention comprises process steps a), b) and c). These process steps are usually carried out in a predetermined order. The method of the present invention optionally comprises additional process steps carried out before, after and / or between the process steps. Process steps b) and c) may be carried out simultaneously; for example, the silane formulation and the additional formulation may be sprayed onto the glass surface simultaneously from two different spraying devices. However, to achieve optimal results, it is preferred to carry out the process steps in a predetermined order.

[0024] In step a) of the method of the present invention, a substrate having at least one glass surface is provided. The substrate is not particularly limited in its form or function, as long as it has at least one glass surface. Optionally, the substrate is made entirely of glass. In one embodiment of the present invention, the substrate consists of at least one glass surface.

[0025] The substrate comprising at least one glass surface is preferably a hollow container, more preferably selected from the group consisting of bottles, thermos, ampoules, tubes, jars, vials and flasks. The substrate is optionally made entirely of glass.

[0026] Glass in the context of the present invention is not particularly limited and includes soda-lime silicate glass, alumosilicate glass, borosilicate glass, alumoborosilicate glass, silica glass, etc., but also includes non-silicate glasses, although these are not preferred.

[0027] Optionally, the method comprises after method step a) and before method step b) the further method step: ai) cleaning at least one glass surface.

[0028] There are numerous methods available to those skilled in the art aimed at, among other things, removing dirt and grease from at least one glass surface. For example, at least one glass surface can be chemically cleaned. Chemical cleaning involves, among other things, treating the surface with an (alkaline) aqueous solution containing a suitable surfactant and / or oxidizing agent. Alternatively, the surface can be wiped with a cloth, which optionally contains the aforementioned aqueous solution.

[0029] In step b) of the method according to the invention, at least one glass surface is treated with a silane formulation. The at least one glass surface may be treated completely or only one or more portions thereof may be treated with the silane formulation. As mentioned above, the silane formulation comprises at least one bis-silyl compound.

[0030] The silane formulation comprises at least one bis-silyl compound comprising at least one building block according to formula (A), said compound being hereinafter referred to as the "bis-silyl compound." Bis-silyl compounds are known in the art and are commercially available or can be prepared by known methods.

[0031] The polyether group is preferably —[CH—CH(R′)—O] j -R" group, where R' is selected from the group consisting of hydrogen and methyl groups, R" is selected from the group consisting of hydrogen, alkyl groups and aryl groups, and j is 1 or an integer ranging from 3 to 100, more preferably from 5 to 20.

[0032] R a1 is preferably selected from the group consisting of hydrogen and C1-C4 alkyl groups. More preferably, R a1 is hydrogen. R a2 is preferably a C1-C8 alkanediyl group, more preferably a C2-C4 alkanediyl group, and even more preferably a 1,3-propanediyl group. a3 is preferably selected from the group consisting of hydrogen and C1-C4 alkyl groups. More preferably, R a3 is hydrogen.

[0033] R a1 is selected from the group consisting of hydrogen and C1-C4 alkyl groups (more preferably, each R a1 is hydrogen), R a2 is a C2-C4 alkanediyl group (each R a2 is more preferably a 1,3-propanediyl group, and R a3is selected from the group consisting of hydrogen and C1-C4 alkyl groups (each R a3 is more preferably hydrogen). This particular preferred option for at least one building block according to formula (A) is referred to as particular preferred option A1. a1 is hydrogen and R a2 is a 1,3-propanediyl group, and R a3 It is further preferred that is hydrogen. This particular preferred choice for at least one building block according to formula (A) is referred to as particular preferred choice A2.

[0034] m is preferably selected from 0, 1 and 2. n is preferably selected from 0, 1 and 2. Preferably, at least one of m and n is less than 3.

[0035] Preferably, the bis-silyl compound has the formula (B) [ka] During the ceremony, Each R b1 are independently selected from the group consisting of hydrogen, alkyl groups, and aryl groups; R b2 is an alkyl group, R b3 is an alkanediyl group, R b4 is selected from the group consisting of hydrogen, alkyl groups, aryl groups, and alkaryl groups; Each R b5 are independently an alkanediyl group, R b6 is selected from the group consisting of hydrogen, alkyl groups, aryl groups, and alkaryl groups; R b7 is selected from the group consisting of hydrogen and alkyl groups; b is selected from 0 and 1; c is selected from 0, 1 and 2; d is selected from 0, 1 and 2; However, the sum of b and c is in the range of 0 to 2. (in addition to at least one building block according to formula (A)).

[0036] The additional building block according to formula (B) in the bis-silyl compound advantageously further improves the wet scratch resistance of glass surfaces treated with the silane formulation (see examples).

[0037] When the bis-silyl compound comprises at least one building block according to formula (B), at least one of m and n is less than 3.

[0038] Preferably, R b1 is preferably selected from the group consisting of hydrogen and C1-C4 alkyl groups. More preferably, R b1 is hydrogen. R b2 is preferably a C1-C4 alkyl group, and R b2 is more preferably a methyl group. R b3 is preferably a C1 to C8-alkanediyl group, more preferably a C2 to C4-alkanediyl group, and even more preferably 1,3-propanediyl. R b4 is preferably selected from the group consisting of hydrogen, alkyl groups and aryl groups, more preferably selected from hydrogen and C1-C4 alkyl groups, and R b4 is even more preferably hydrogen. Preferably, R b5 is a C1-C8-alkanediyl group, more preferably a C2-C4-alkanediyl group, and even more preferably a 1,2-ethanediyl group. R b6 is preferably selected from the group consisting of hydrogen, alkyl groups and aryl groups, more preferably selected from hydrogen and C1-C4 alkyl groups, and R b6 is even more preferably hydrogen. R b7is preferably selected from the group consisting of hydrogen, alkyl groups and aryl groups, more preferably selected from hydrogen and C1-C4 alkyl groups, and R b7 is even more preferably hydrogen. b4 , R b6 and R b7 Even more preferably, is hydrogen. b is preferably 0. c is preferably selected from 0 and 1. d is preferably 0.

[0039] A particularly preferred embodiment of at least one building block according to formula (B) is of formula (B1) [ka] During the ceremony, Each R b11 are independently selected from the group consisting of hydrogen and C1-C4-alkyl groups; R b13 is a C2-C4-alkanediyl group, even more preferably 1,3-propanediyl, R b14 is selected from the group consisting of hydrogen and C1-C4 alkyl groups, and R b14 is even more preferably hydrogen, R b17 is selected from the group consisting of hydrogen and C1-C4 alkyl groups, and R b17 is even more preferably hydrogen, c' is selected from 0, 1 and 2 R is a building block described in b11 , R b14 and R b17 It is preferred that all of are hydrogen.

[0040] The building block according to formula (B1) is a preferred alternative to the aforementioned building block according to formula (B). The building block according to formula (B1) is preferably used as the sole alternative to the latter, or (less preferred) both building blocks are used in combination. Since very good results can be obtained, it is preferred that at least one bis-silyl compound comprises (or consists of) at least one building block according to formula (A) using the above-mentioned specific preferred selection A1 and at least one building block according to formula (B1). Since optimal results can be obtained, it is more preferred that at least one bis-silyl compound comprises (or consists of) at least one building block according to formula (A) using the above-mentioned specific preferred selection A2 and at least one building block according to formula (B1).

[0041] The total number of building blocks according to formula (A) and, if present, the total number of building blocks according to formula (B) in the bis-silyl compound is preferably in the range of 2 to 1000, more preferably 3 to 500, even more preferably 4 to 100, and even more preferably 5 to 50.

[0042] Preferably, the numerical ratio of building blocks according to formula (A) to building blocks according to formula (B) in the bis-silyl compound is in the range of 1 (building blocks according to formula (A)) to 0.1-1000 (building blocks according to formula (B)), more preferably 1 to 1-250, even more preferably 1 to 1-50, and even more preferably 1 to 1-10, to provide optimal wet scratch resistance of such treated glass surfaces over a wide range of concentrations of bis-silyl compounds present in the silane formulation. The number or ratio of building blocks can be determined by standard means, e.g., 1 H, 13 C and / or 29 It can be determined by Si-NMR spectroscopy. Those skilled in the art will be aware of further suitable methods, such as gel permeation chromatography.

[0043] At least one building block according to formula (A) and (if contained in the bis-silyl compound) at least one building block according to formula (B) preferably constitute at least 50% by weight of the bis-silyl compound, more preferably 75% by weight, and even more preferably 90% by weight. The bis-silyl compound most preferably consists of one or more building blocks according to formula (A) and optionally one or more building blocks according to formula (B).

[0044] Preferably, at least one bis-silyl compound is an oligomer or polymer, since improved crosslink density of the film obtained from the bis-silyl compound can be obtained. Improved crosslink density leads to improved dry and wet scratch resistance of the treated surface. Oligomers according to the present invention comprise 2 to 4 (total) building blocks according to formula (A) and (optionally) (B), and polymers comprise at least 5 (total) building blocks according to formula (A) and (optionally) (B). Non-limiting examples of oligomers comprising one building block according to formula (A) and (B) are shown below: [ka]

[0045] Oligomers and polymers typically comprise one or more of linear, branched, and cyclic structures (said structures being formed by building blocks according to formula (A) and / or (B)). The building blocks described herein can also be understood as structural repeat units when two or more building blocks according to formula (A) and optionally (B) are comprised by a bis-silyl compound. When at least one bis-silyl compound is an oligomer or polymer, the building blocks contained in the at least one bis-silyl compound, i.e., the building blocks according to formula (A) and (if present) (B), can be arranged in various patterns. The pattern formed by the building blocks can include alternating, block, and / or random patterns. When two or more building blocks according to formula (A) and optionally (B) are comprised by a bis-silyl compound, they typically comprise a bonded oxygen atom (O in the chemical formula) between the silicon atoms of each building block. y / 2 and y represents one of (3-m), (3-n), (3-bc) or (3-c').

[0046] As is conventional in the art, R g -SiO (4-g / 2)It should be understood that the depicted silicon atom has (4-g) oxygen atoms (where g is an integer ranging from 0 to 4) and g residues R. The oxygen atom is bonded to the silicon atom by a single bond and therefore has another substituent, such as the silicon atom of the unity described above. In the present invention, the other silicon atom is preferably one of the building blocks described in formula (A) or (B). When g is 3, an M unit is present. When g is 2, a D unit is present. When g is 1, a T unit is present. When g is 0, a Q unit is present. This nomenclature is known to those skilled in the art, for example, see W. Noll, Chemie und Technologie der Silicone, Verlag Chemie, Weinheim Bergstr., 1960, p. 2 et seq.

[0047] An alternative representation of the building blocks described in formula (A) is as follows: [ka]

[0048] This alternative representation of the building block according to formula (A) is represented by "O" in the above notation. (3-h / 2) The free valences of these oxygen atoms (indicated by the bond to the wavy line) can be filled with any suitable partner, preferably with silicon atoms of other building blocks according to formula (A) or (B). When the free valences are filled with silicon atoms of other building blocks according to formula (A) and / or (B), the bis-silyl compound is an oligomer or polymer.

[0049] Similarly, an alternative representation of the building block according to formula (B) can be written as follows: [ka]

[0050] Below, an exemplary oligomer of a bis-silyl compound consisting of three building blocks according to formula (A) is shown. In this representation, the three building blocks are highlighted by dashed rectangular boxes to further clarify the concept of building blocks. The building blocks are connected by bridging oxygen atoms. [ka]

[0051] As is known in the art, bis-silyl compounds can be prepared by reacting bis-(trialkoxysilylpropyl)amine and, optionally, one or more amino-functional silanes, such as AMEO, and condensing them. Upon condensation of the aforementioned silanes, the alkoxy groups are advantageously cleaved to form siloxane bonds ("Si-O-Si") as shown above. These siloxane bonds contain a bridging oxygen atom located between the two silicon atoms of each building block.

[0052] The amount of the at least one bis-silyl compound in the silane formulation is preferably in the range of 0.001 to 10 wt. %, more preferably 0.01 to 4 wt. %, even more preferably 0.05 to 1 wt. %, and even more preferably 0.1 to 0.8 wt. %, based on the total silane formulation. When two or more bis-silyl compounds are included in the silane formulation, the amount of all bis-silyl compounds is preferably in the range defined above.

[0053] The silane formulation preferably includes at least one acid, which advantageously improves the stability of the silane formulation. The acid typically has a pK high enough to transfer a proton onto another component in the silane formulation. a The at least one acid is typically selected from inorganic acids and organic acids. Preferred inorganic acids are selected from the group consisting of nitric acid, hydrochloric acid, methanesulfonic acid, and mixtures thereof.

[0054] Organic acids are preferred, preferably selected from the group consisting of monocarboxylic acids and dicarboxylic acids. The acids are preferably unsubstituted. Monocarboxylic acids are more preferred as the at least one acid, because they surprisingly improve the wetting of the glass surface of the substrate, thus improving the beneficial effects of the present invention. Even more preferably, the at least one acid is a monocarboxylic acid having 1 to 4 carbon atoms, and even more preferably, the at least one acid is selected from acetic acid and formic acid. Because of its superiority in this respect, formic acid is most preferred in this context.

[0055] The amount of the at least one acid depends, inter alia, on the amine number of the bis-silane compound. Typically, the amount of the at least one acid ranges from 0.00001 to 10 wt. %, preferably from 0.01 to 1 wt. %, and more preferably from 0.2 to 0.1 wt. %, based on the total silane formulation.

[0056] The silane formulation preferably comprises water in an amount of preferably 1 to 99.9 wt. %, more preferably 5 to 90 wt. %, even more preferably 10 to 80 wt. %, based on the total silane formulation.

[0057] The silane formulation optionally includes at least one organic solvent. Any organic solvent suitable for dissolving or dispersing the components of the silane formulation can be used. The at least one organic solvent is preferably a polar solvent, more preferably an alkanol, and even more preferably a C1-C4 alkanol. The one or more optional organic solvents are preferably contained in a total amount of 25% by weight or less, more preferably 20% by weight or less, even more preferably 15% by weight or less, and even more preferably 1.0% by weight or less, based on the total silane formulation. Ideally, the amount is less than 0.1% by weight, as this further improves the ecological effectiveness of the present invention.

[0058] Ideally, the silane formulation is a solution, preferably an aqueous solution, which facilitates the treatment of at least one glass surface with the silane formulation by avoiding clogging of the nozzle of the spray application device, especially when the silane formulation is applied by spraying. Alternatively, the silane formulation is a dispersion, preferably a microemulsion. In the latter case, the silane formulation includes at least one emulsifier. The at least one emulsifier and its amount can be selected based on the general knowledge and routine experimentation of those skilled in the art. In this case, useful emulsifiers can be selected from the emulsifiers described for the additional formulations (see below).

[0059] The pH value of the silane formulation is typically in the range of 1 to 14. The pH value is preferably in the range of 2 to 7, more preferably 3 to 5, which results in improved stability of the silane formulation.

[0060] The solids content of the silane formulation is preferably in the range of 0.01 to 15%, more preferably 0.05 to 10%, and even more preferably 0.1 to 1%.

[0061] The viscosity of the silane formulation is preferably in the range of 0.1 to 100,000 mPas, more preferably 0.5 to 100 mPas, and even more preferably 1 to 5 mPas. Silane formulations having a viscosity within the above ranges can be easily applied by spray application, particularly without the risk of clogging the nozzle of a spray application device.

[0062] The silane formulation can be prepared by standard and known means in the art. Illustratively, the aforementioned components can be mixed in a suitable container using standard means. At least one bis-silyl compound is known in the art and commercially available. For example, an oligomeric or polymeric bis-silyl compound can be prepared by hydrolysis and condensation of bis-(trialkoxysilylpropyl)amine and, optionally, one or more amino-functional silanes, such as AMEO. The alcohol obtained during the preparation is preferably removed by distillation.

[0063] The silane formulation comprises, in addition to at least one bis-silyl compound, a silane compound of formula (I) [ka] During the ceremony, Each R y1 are independently selected from the group consisting of hydrogen, alkyl groups, polyether groups, and aryl groups; R y2 is an alkyl group, R y3 is an alkanediyl group, R y4 is selected from the group consisting of hydrogen, alkyl groups, aryl groups, and alkaryl groups; Each R y5 are independently an alkanediyl group, R y6 is selected from the group consisting of hydrogen, alkyl groups, aryl groups, and alkaryl groups; R y7 is selected from the group consisting of hydrogen and alkyl groups; f is selected from 0, 1 and 2; g is selected from 0 and 1; h is selected from 0, 1 and 2; However, the sum of f and g is preferably in the range of 0 to 2. Preferably, the compound comprises at least one silane-based compound containing at least one building block according to the formula:

[0064] The silane-based compound further improves wet scratch resistance. It is preferred that the silane-based compound is contained in the silane formulation, especially when at least one bis-silyl compound contains only the building block described in formula (A) or consists only of the building block described in formula (A). The silane-based compound preferably does not contain the building block described in formula (A).

[0065] R y1 is preferably selected from the group consisting of hydrogen and C1-C4-alkyl groups. R y3 is preferably a C2-C4 alkanediyl group. R y4 is preferably selected from the group consisting of hydrogen and C1-C4-alkyl groups. R y7 is preferably selected from the group consisting of hydrogen and C1-C4-alkyl groups. g is preferably 0. h is preferably 0.

[0066] In a preferred embodiment of the present invention, R y1 is selected from the group consisting of hydrogen and C1-C4 alkyl groups, and R y3 is a C2-C4-alkanediyl group, and R y4 is selected from the group consisting of hydrogen and C1-C4 alkyl groups, and R y7 is selected from the group consisting of hydrogen and C1-C4-alkyl groups; g is 0; f is selected from 0, 1 and 2; and h is 0.

[0067] At least one building block according to formula (I) preferably constitutes at least 50% by weight of the silane-based compound, more preferably 75% by weight, and even more preferably 90% by weight. The silane-based compound most preferably consists of one or more building blocks according to formula (I). The number or ratio of building blocks can be determined by standard means, for example: 1 H, 13 C and / or 29 It can be determined by Si-NMR spectroscopy. Those skilled in the art will be aware of further suitable methods, such as gel permeation chromatography.

[0068] In the silane formulation, the amount of silane-based compound is preferably in the range of 0.001 to 20 wt %, more preferably 0.01 to 8 wt %, even more preferably 0.05 to 2 wt %, and even more preferably 0.1 to 1.6 wt %, based on the total silane formulation.

[0069] Silane-based compounds are known in the art and commercially available. Useful preparation methods are described, inter alia, in U.S. Patent Application Publication No. 2018 / 127442 (especially paragraphs 11-41 and Examples 1, 2, and 3).

[0070] The at least one silane-based compound is preferably an oligomer or a polymer, for the same reasons as outlined for the at least one bis-silyl compound. The details given for the building block pattern described for the at least one bis-silyl compound apply mutatis mutandis to the at least one silane-based compound.

[0071] The weight ratio of the at least one silane compound to the at least one bis-silyl compound, when the first-mentioned compound is present in the silane formulation according to the invention, is preferably in the range of 0.1 to 0.9, more preferably 0.2 to 0.8, even more preferably 0.3 to 0.7.

[0072] In one embodiment of the present invention, the silane formulation comprises, preferably in the amounts previously described herein, at least one bis-silyl compound, at least one acid, -water, optionally at least one organic solvent In this embodiment, the preferences outlined herein above apply mutatis mutandis.

[0073] In a preferred embodiment of the present invention, the silane formulation comprises, preferably in the amounts previously described herein, at least one bis-silyl compound, at least one acid, -water, at least one silane-based compound optionally at least one organic solvent In this embodiment, the preferences outlined herein above apply mutatis mutandis.

[0074] The temperature of the at least one glass surface in process step b) is preferably in the range of 20 to 200°C, more preferably 60 to 150°C, and even more preferably 100 or 110 to 130°C. Therefore, it is not necessary to heat the glass surface to high temperatures, as is the case with commonly used tin compounds. Therefore, the process according to the invention is energy-saving and more environmentally friendly.

[0075] Optionally, the temperature of the silane formulation is adjusted to a value in the range of 10 to 80°C, preferably 20 to 30°C, before the silane formulation is used to treat at least one glass surface with the silane formulation.

[0076] Generally, it is desirable to maintain the temperature difference between the silane formulation (or the additional formulation in method step c)) and the glass surface within a certain range. For example, a temperature difference between the additional formulation and the glass surface of 100°C or more should be avoided. Otherwise, the glass surface may be damaged or otherwise subjected to treatment. The acceptable temperature difference depends particularly on the type of glass used. Those skilled in the art will know this and will select an appropriate temperature based on general knowledge or routine experimentation.

[0077] In method step c), at least one glass surface is treated with an additional compound. The additional compound comprises at least one lubricant. Lubricants useful for this purpose are known in the art and can be selected by those skilled in the art through routine experimentation. At least one lubricant is preferably selected from the group consisting of wax, fatty acid and fatty acid ester. More preferably, at least one lubricant is selected from the group consisting of wax, fatty acid and fatty acid ester. Even more preferably, at least one lubricant is a wax. The preferences outlined allow for increased scratch resistance.

[0078] Wax is preferably used as aqueous dispersion.Generally, any wax that can be dispersed in water can be used in the present invention.Wax is preferably selected from natural wax and synthetic wax.Natural wax includes modern wax such as beeswax, carnauba wax or candelilla wax, fossil wax such as montan wax or its derivative, and petroleum wax (both paraffin wax and microcrystalline wax).Generally, when additional formulation is dispersion (for example, emulsion), additional formulation preferably comprises at least one emulsifier that is selected by those skilled in the art through routine experimentation or based on the general knowledge of those skilled in the art (see below).

[0079] The synthetic wax is preferably selected from the group consisting of Fischer-Tropsch wax, polyolefin wax (such as polyethylene wax, polypropylene wax, polyisobutylene wax and copolymers thereof), amide wax (e.g., N,N'-distearoylethylenediamine), polyethylene glycol wax and polypropylene glycol wax. More preferably, the synthetic wax is a polyolefin wax or a copolymer thereof, even more preferably a polyolefin wax, and even more preferably a polyethylene wax.

[0080] In one embodiment of the present invention, the at least one lubricant is a wax, preferably the at least one lubricant is selected from the group consisting of amide waxes, polyolefin waxes and copolymers of polyolefin waxes, more preferably the at least one lubricant is a polyolefin wax or a copolymer thereof, even more preferably a polyolefin wax, and even more preferably a polyethylene wax.

[0081] Non-polar waxes such as petroleum waxes, Fischer-Tropsch waxes and polyolefin waxes are preferably used in their oxidized form for better dispersibility. Such oxidized waxes have been known for some time.

[0082] In the present invention, polyethylene wax "polyethylene" (sometimes referred to in the art as "polyethylene") is particularly preferred. The polyethylene waxes used generally have a number average molecular weight (M) in the range of 400 to 20,000 g / mol (as measured by GPC, PLgel column (Agilent), solvent: 1,2,4-trichlorobenzene + 0.015 wt% butylated hydroxytoluene, 160°C, using polyethylene standards provided by Agilent). n ) Preferably, M n is in the range of 500 to 15,000 g / mol, more preferably 1000 to 8000 g / mol, which provides improved stability and enhanced scratch resistance of the additive formulation.

[0083] The melting point of the polyethylene wax is preferably in the range of 50 to 170°C, preferably 80 to 150°C, more preferably 100 to 135°C. The melting point is measured according to DIN 51532 (2012). Said range provides improved stability and enhanced scratch resistance of the additive formulation.

[0084] There are many methods known to those skilled in the art for preparing polyethylene waxes. Various types of them are also commercially available in the form of aqueous dispersions. Illustratively, polyethylene waxes can be prepared by thermal decomposition and, where appropriate, free radical decomposition of higher molecular weight polyethylenes, or by polymerization of ethylene, either by a free radical mechanism or by transition metal catalysis.

[0085] Polyethylene waxes optionally have some degree of branching which may also result from the use of olefinic comonomers such as propene, 1-butene or 1-hexene in the case of short chain branching.

[0086] To produce a dispersion suitable for the present invention, it is preferable to use as a starting material a partially oxidized polyethylene wax, which may be further esterified and / or saponified if desired. Many types of such polyethylene waxes are commercially available. Furthermore, it is possible to use copolymers containing 50 mol% or more of ethylene and 50 mol% or less of a polar monomer, such as ethylene-vinyl acetate copolymer wax or a copolymer of ethylene and acrylic acid. Another possible method for preparing dispersible polyethylene is to graft polyethylene in the melt with an unsaturated polar monomer, such as maleic anhydride. For this purpose, it is generally useful to add a free-radical initiator.

[0087] The polyethylene waxes thus modified can be converted, if desired after further modification, into nonionic, anionic or cationic dispersions by conventional methods, usually with the addition of one or more emulsifiers.

[0088] There are many commercially available (partial) fatty acid esters, preferably so-called ester waxes, which can be used as at least one lubricant. Preferred examples include stearic acid esters of ethylene glycol, diethylene glycol, polyethylene glycol or 1,4-butanediol or glyceryl tristearate, as well as mixed partial esters of mannitol with stearic and palmitic acids.

[0089] At least one fatty acid suitable as a lubricant has the structure R x -COOH, wherein R x is a C10-C22 alkyl or C10-C22 alkenyl group. Preferred examples are oleic acid, stearic acid, palmitic acid and lauric acid.

[0090] Within the context of the present invention, it is possible to use mixtures of lubricants, for example waxes and fatty acids or waxes and (partial) fatty acid esters or fatty acids and (partial) fatty acid esters or any other combination.

[0091] The additional formulation optionally comprises at least one solvent, and the at least one solvent is preferably selected from the group consisting of water, organic solvent and their mixture.If desired, the organic solvent described hereinabove can be used.More preferably, the at least one solvent is water because of its ecologically friendly characteristics.

[0092] The amount of at least one lubricant in the additional formulation is preferably in the range of 0.05 to 5% by weight, more preferably 0.1 to 2% by weight, based on the additional formulation. When two or more lubricants are used in the additional formulation, the total amount of all lubricants is preferably in the above range.

[0093] In general, especially when the additional formulation is a dispersion (e.g., emulsion), the additional formulation preferably contains at least one emulsifier (also known in the art as a surfactant or wetting agent). The at least one emulsifier and its amount can be selected based on the general knowledge and routine experimentation of those skilled in the art. The at least one emulsifier is preferably contained in the additional formulation in an amount of 0.01 to 10% by weight, more preferably 0.1 to 2.5% by weight, and even more preferably 0.2 to 1.0% by weight, based on the total additional formulation. When two or more emulsifiers are contained, the total amount of all emulsifiers is preferably within the range defined above. Preferably, the at least one emulsifier has an HLB value of 8 or more, more preferably 11 or more.

[0094] Useful emulsifiers are selected from the group consisting of nonionic, anionic, cationic, amphoteric emulsifiers and mixtures thereof. Preferably, the at least one emulsifier is selected from the group consisting of nonionic, anionic, cationic emulsifiers and mixtures thereof, more preferably from the group consisting of nonionic and cationic emulsifiers and mixtures thereof.

[0095] Preferred examples of nonionic emulsifiers are those represented by formula (E): [ka] During the ceremony, R E1 is a C8-C22 alkyl group, R E2 is selected from the group consisting of hydrogen, alkyl groups, hydroxyl groups, and oxyalkyl groups; each E is independently an alkanediyl group; e is an integer ranging from 1 to 100 is expressed by

[0096] R E1 is preferably a C10 to C18 alkyl group, more preferably a C12 to C16 alkyl group. E1 is a branched alkyl group. Most preferably, R E1 is an iso-C13-alkyl group. E2 is preferably selected from the group consisting of a hydroxyl group, an oxymethyl group, and a methyl group. More preferably, R E2 is a hydroxyl group. E is preferably selected from the group consisting of a 1,2-ethanediyl group, a 1,2-propanediyl group, and a 1,3-propanediyl group. e is preferably in the range of 2 to 10, preferably 3 to 7, and more preferably 4 to 6.

[0097] Preferably, the anionic emulsifier is of formula (L) [ka] During the ceremony, RL is a C8-C22 alkyl group, L is selected from the group consisting of a carboxylic acid group (-CO2H), a sulfonic acid group (-SO3H) and a phosphonic acid group (-PO3H2) or a salt thereof. It is expressed by R L is preferably a C10 to C18 alkyl group, more preferably a C12 to C16 alkyl group. L is a branched alkyl group. L is preferably a sulfonic acid group or a salt thereof.

[0098] The cationic emulsifier preferably has the formula (T) [ka] During the ceremony, R T is a C8-C22 alkyl group, T is a cationic group, preferably -NR k 4 + is a group, and R k is hydrogen or an alkyl group such as a methyl or ethyl group (preferred). T is preferably a C10 to C18 alkyl group, more preferably a C12 to C16 alkyl group.

[0099] Preferably, the additional formulation contains colloidal silica in an amount ranging from 0.01 to 1% by weight, preferably from 0.05 to 0.5% by weight, more preferably from 0.1 to 0.25% by weight, based on the total weight of the additional formulation (and the solids content of the colloidal silica if a dispersion is used). 50 ) is preferably in the range of 10 to 250 nm, more preferably 20 to 100 nm. 50 Values ​​can be measured by dynamic light scattering, preferably using a Malvern Panalytical according to ISO22412:2017-02. Colloidal silica can improve the stability of additional formulations.

[0100] Optionally, the additional formulation comprises an organic polymer selected from the group consisting of polyurethanes, polyesters, polymethacrylates, and mixtures and copolymers thereof. The amount of organic polymer is preferably in the range of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.25 to 1% by weight, based on the additional formulation. The organic polymer improves the adhesion of labels, paints, or inks applied to the surface after the additional formulation has been applied.

[0101] At least one glass surface is treated with the silane formulation and the additional formulation by conventional means. Preferably, the treatment of the at least one glass surface in process steps b) and c) is carried out independently by spraying, dipping, rolling, painting, and combinations of the above. In both process steps, spraying is preferred.

[0102] The temperature of the at least one glass surface in method step c) is independently preferably in the range of 20 to 200°C, more preferably 60 to 150°C, even more preferably 100 or 110 to 130°C.

[0103] Optionally, the temperature of the additional formulation is adjusted to a value in the range of 10 to 80°C, preferably 20 to 30°C, before the additional formulation is used to treat at least one glass surface with the additional formulation.

[0104] Preferably, the method of the present invention does not use any tin compounds, such as tin salts such as n-butyltin trichloride and tin tetrachloride. Therefore, the silane formulation preferably does not contain any (intentionally added) tin compounds. Furthermore, the additional formulation preferably does not contain any (intentionally added) tin compounds. This means that the content of tin compounds in the silane formulation and the additional formulation is preferably 0.1% by weight or less, more preferably 0.01% by weight or less, and even more preferably 0.001% by weight or less. Ideally, the silane formulation and the additional formulation are completely free of tin compounds. In particular, the method of the present invention does not use any tin compounds to bond at least one lubricant to at least one glass surface. The omission of tin compounds, such as tin salts, is environmentally and toxicologically advantageous, as already outlined herein.

[0105] In another aspect of the present invention, the silane formulation is used as an adhesion promoter to at least one lubricant on the glass surface of a substrate, particularly in a cold end coating process, wherein the at least one lubricant is preferably selected from the group consisting of waxes, fatty acids and fatty acid esters.

[0106] In yet another aspect, the present invention further provides a method for producing a i) at least one glass surface; ii) at least one silane-based layer (hereinafter "layer ii") obtained by treating said at least one glass surface with a silane formulation as previously described herein; iii) at least one additional layer (hereinafter "layer iii") on the silane-based layer comprising at least one lubricant selected from the group consisting of waxes, fatty acids, fatty acid esters, and wetting agents; The present invention relates to a substrate comprising:

[0107] Layer ii) is obtained by treating at least one glass surface with the silane formulation described hereinabove. Layer ii) has proven difficult to characterize. The inventors believe that a number of compounds derived from at least one bis-silyl compound are present in layer ii). Layer iii) is obtained by treating at least one glass surface (after the formation of layer ii) thereon) with an additional formulation.

[0108] The substrate optionally comprises one or more additional layers located below layers ii) and iii) (i.e., between layer ii) and at least one glass surface), above layers ii) and iii), or between layers ii) and iii). Preferably, the optional additional layer is located on layer iii). Layers ii) and iii) are preferably disposed directly on each other. Layer ii) is preferably disposed directly on at least one glass surface. Layer ii) is present on the entire glass surface or only on one or more portions thereof. Layer iii) is present on the entire surface of layer ii) or only on one or more portions of the surface of layer ii). Optionally, the substrate comprises one or more adhesive layers on layer iii). Conventional adhesives can be used for this purpose without limitation. A label is optionally disposed on the optional adhesive layer. The label is usually made of paper or the like and can be printed on its outer surface.

[0109] Preferably, the substrate is a hollow vessel, more preferably a hollow vessel selected from the group consisting of a bottle, a thermos, an ampoule, a tube, a jar, a vial, and a flask.

[0110] In yet another aspect of the present invention, the substrate according to the present invention, in particular the hollow container as substrate, is used to store a fluid or solid therein, preferably a fluid, more preferably a liquid, even more preferably a beverage such as water.

[0111] In yet another aspect, the present invention relates to a kit of parts, said kit of parts comprising: P1) Formula (A) [ka] During the ceremony, Each R a1 are independently selected from the group consisting of hydrogen, alkyl groups, and aryl groups; Each R a2 are independently an alkanediyl group, R a3 is selected from the group consisting of hydrogen, alkyl groups, and aryl groups; m is an integer ranging from 0 to 3; n is an integer ranging from 0 to 3 a presilane formulation comprising at least one bis-silyl compound containing at least one building block according to P2) A pre-addition formulation comprising at least one lubricant selected from the group consisting of waxes, fatty acids and fatty acid esters. Includes.

[0112] P1 preferably comprises at least one bis-silyl compound, at least one silane-based compound, at least one acid and water.

[0113] The presilane formulation may be the same as the silane formulation previously described herein. However, it is preferred that the presilane formulation be more concentrated. Therefore, to save on transportation costs, the amount of at least one bis-silyl compound and at least one optional acid is preferably higher, while the amount of solvent (if present), i.e., at least one organic solvent and water, is lower compared to the silane formulation. To that end, the amount of at least one bis-silyl compound in the presilane formulation is preferably in the range of 5% to 25% by weight, more preferably 10 to 20% by weight.

[0114] The amount of the at least one acid in the Presilane formulation is preferably at least 0.1 wt%, more preferably 0.15 wt%, and even more preferably 0.2 wt%.

[0115] The pre-additional formulation may be the same as the pre-additional formulation described hereinabove. However, in order to save on transportation costs, it is preferred that the amount of at least one lubricant is higher, while the amount of solvent (if present), i.e., at least one organic solvent and water, is lower. The amount of at least one lubricant in the pre-additional formulation is preferably in the range of 10-50% by weight, preferably 15-40% by weight, more preferably 20-30% by weight.

[0116] The presilane formulation and the pre-additional formulation may be diluted to a desired concentration before use, for example with water and / or at least one organic solvent, preferably with water.

[0117] The invention will now be described by reference to the following non-limiting examples.

[0118] Example Unless otherwise noted below, commercially available products were used as described in the technical data sheets available on the filing date of this application. The most recent version of the specifications was used unless otherwise noted below.

[0119] Untreated 1 L soda lime silicate glass bottles were used as the glass substrate in all experiments. A spray gun (IPOTOOLS Mini HLVP Spray Gun) was used as the manual applicator. Additional formulations in the examples were prepared using a polyethylene dispersion obtained from TotalEnergies and available as Glasskote SC100 E.

[0120] Determination of Dry Residue (Solids Content): The solids content (also called dry residue) of the formulation was determined as follows: a 1.000 g sample was weighed into a small porcelain dish and dried in a drying oven at 105°C until constant weight was reached.

[0121] Amine content determination 150–400 mg of sample (depending on the amine content) was weighed into a 150 ml beaker and dissolved in 90 ml of concentrated acid. Using potentographic detection, the resulting solution was titrated with a solution of perchloric acid in acetic acid (c(HClO) = 0.1 mol / l). The factor of the perchloric acid solution was determined using potassium hydrogen phthalate.

[0122] Calculation:

number

[0123] Determination of free alcohol content in silane formulations: Alcohols were measured by gas chromatography (column: RTX200 (60 m), temperature program: 90°C for 10 minutes, then 25°C / min to 240°C, detector: FID, injection volume: 1.0 µl, internal standard: 2-butanol).

[0124] The pH value was determined according to DIN EN ISO 10523 (2012). The viscosity was measured according to DIN 53015 (2019).

[0125] Comparative Example 1 Under a nitrogen atmosphere, a reactor was charged with 80.0 g of water. 20.0 g of (3-aminopropyl)triethoxysilane was added thereto. The reaction mixture was stirred at 60° C. for 3 hours until the silane was completely hydrolyzed. The resulting formulation containing silane oligomers formed a clear, colorless liquid and had the following analytical and physical data: Solid content: 7.4% by weight Free ethanol content: 13% by weight Amine content as NH2: 1.5 wt% Viscosity: 3,0mPas pH: 11.0

[0126] Comparative Example 2 Comparative Example 1 was repeated using 80 g of an aqueous solution containing 5.4 g of 85 wt. % formic acid instead of water. The resulting formulation containing silane oligomer formed a clear, colorless liquid and had the following analytical and physical data: Solid content: 12% by weight Free ethanol content: 13% by weight Amine content as NH2: 1.48 wt% Viscosity: 2.9mPas pH: 4.5

[0127] Comparative Example 3 Comparative Example 1 was repeated using 20 g of (3-aminopropyl)dimethoxymethylsilane in place of the above silane. The resulting formulation containing the silane oligomer formed a clear, colorless liquid and had the following analytical and physical data: Solid content: 14.4% by weight Free methanol: 7.9% by weight Amine content as NH2: 1.97% by weight Viscosity: 3mPas pH: 11.2

[0128] Preparation Example 1 Under a nitrogen atmosphere, 80 g of an aqueous solution containing 5.4 g of 85 wt. % formic acid (aq.) was charged into a reactor. 19.8 g of (3-aminopropyl)triethoxysilane and 0.2 g of bis[3-(triethoxysilyl)propyl]amine were added to the solution. The reaction mixture was stirred at 60° C. for 3 hours until the silane was completely hydrolyzed. The resulting formulation containing the bis-silyl compound formed a clear, colorless liquid and had the following analytical and physical data: Solid content: 12.1% by weight Free ethanol content: 13.0% Amine content as NH2: 1.48% Viscosity: 2.9mPas pH: 4.5

[0129] Preparation Example 2 Preparative Example 1 was repeated using 80 g of an aqueous solution containing 19.0 g of (3-aminopropyl)triethoxysilane and 1.0 g of bis[3-(triethoxysilyl)propyl]amine and 5.0 g of 85 wt % formic acid (aq.). The formulation thus obtained containing the bis-silyl compound formed a clear, colorless liquid and had the following analytical and physical data: Solid content: 12.0% by weight Free ethanol content: 13% Amine content as NH2: 1.44% Viscosity: 2.9mPas pH: 4.7

[0130] Preparation Example 3 Preparative Example 1 was repeated using 80 g of an aqueous solution containing 18.0 g of (3-aminopropyl)triethoxysilane and 2.0 g of bis[3-(triethoxysilyl)propyl]amine and 5.1 g of 85 wt. % formic acid (aq.). The resulting formulation containing the bis-silyl compound formed a clear, colorless liquid and had the following analytical and physical data: Solid content: 12.3% by weight Free ethanol content: 12% Amine content as NH2: 1.4% Viscosity: 3.0mPas pH: 4.4

[0131] Preparation Example 4 Preparative Example 1 was repeated using 80 g of an aqueous solution containing 16.0 g of (3-aminopropyl)triethoxysilane and 4.0 g of bis[3-(triethoxysilyl)propyl]amine and 5.1 g of 85 wt % formic acid (aq.). The formulation thus obtained containing the bis-silyl compound formed a clear, colorless liquid and had the following analytical and physical data: Solid content: 12.1% by weight Free ethanol content: 12% Amine content as NH2: 1.3% Viscosity: 3.2mPas pH: 4.2

[0132] Preparation Example 5 Preparative Example 1 was repeated using 85 g of an aqueous solution containing 7.5 g of (3-aminopropyl)triethoxysilane and 7.5 g of bis[3-(triethoxysilyl)propyl]amine and 3.9 g of 85 wt % formic acid (aq.). The formulation thus obtained containing the bis-silyl compound formed a clear, colorless liquid and had the following analytical and physical data: Solid content: 10.7% by weight Free ethanol content: 9.4% Amine content as NH2: 0.84% Viscosity: 2.8mPas pH: 3.9

[0133] Preparation Example 6 (100% of the building block according to formula (A)) Under a nitrogen atmosphere, 85 g of an aqueous solution containing 2.0 g of 85 wt. % formic acid (aq.) was charged into a reactor. 15.0 g of bis[3-(triethoxysilyl)propyl]amine was added to the solution. The reaction mixture was stirred at 60° C. for 3 hours until the silane was completely hydrolyzed. The resulting formulation containing the bis-silyl compound formed a clear, colorless liquid and had the following analytical and physical data: Solid content: 8.6% by weight Free ethanol content: 9.5% Amine content as NH2: 0.6% Viscosity: 12.6mPas pH: 4.5

[0134] Application of the silane formulation (corresponding to method step b) The product mixtures obtained as described in Preparative Examples 1-6 were diluted with deionized water in the ratios given in the table below (hereinafter referred to as "dilution factors"), thereby preparing silane formulations ready for immediate use.

[0135] Similarly, comparative formulations containing silane oligomers were obtained by diluting the product mixtures obtained as Comparative Examples 1-3 with DI water in the ratios (hereinafter referred to as "dilution factors") given in the table below.

[0136] The glass substrates were treated by spray coating using a manual applicator. For this purpose, the bottles were rotated once while treating their entire surface. Before the treatment described, the bottles were heated in an oven to the temperatures given in Tables 1 and 2 below. The spray conditions were as follows: Nozzle diameter: 0.5 mm Applicable pressure: 4 bar Spray distance: 20cm Spray amount: 20ml / min Rotation time: approx. 6-7 seconds

[0137] Application of additional formulation (corresponding to method step c) The glass substrates were coated by spray coating using a manual applicator. For this purpose, the bottles were rotated twice while treating the entire surface. Before the treatment described, the bottles were heated in an oven to the temperature given below. Additional formulations were prepared by diluting Glasskote SC100E with deionized water to the concentrations given below. The spray conditions were as follows: Temperature: 90℃ Polyethylene concentration: 0.28% by weight Nozzle diameter: 0.8 mm Applicable pressure: 4 bar Spray distance: 20cm Spray amount: 20ml / min Each rotation takes about 10 seconds

[0138] Test Method Dry and Wet Scratch Resistance - Scratch Test Scratch resistance was tested by rubbing the surfaces of two coated glass bottles against each other, with one bottle in each hand. The test was repeated several times by at least two people in different areas of the glass bottle. Any instances of scratch resistance or slippage were recorded. Wet scratch resistance was tested in the same way as dry scratch resistance, but with the glass surface pre-wetted with water. For that purpose, the glass surface was wetted under running water (until wet). The pressure and scratch time (15 seconds) were kept constant. Ranking: No scratches: 1, slight scratches: 2, scratches across the entire test surface: 3

[0139] Optical Appearance The optical appearance was visually inspected by at least two people and was ranked by turbidity using the following criteria: clear (1), slightly hazy (2), and hazy (3).

[0140] Label adhesion A paper label was glued onto the treated glass bottle using a standard adhesive (Turmerleim ST 50 KF, a standard casein-based label adhesive). The paper label was allowed to cure for 7 days at room temperature (20°C). The label was then peeled off by hand.

[0141] The ranking was as follows: no delamination (tear of fibers) = 1 (good), partial delamination = 2 (acceptable) and complete delamination = 3 (unacceptable). [Table 1] [Table 2]

[0142] The results clearly show that the method according to the invention improves the scratch resistance of the treated glass surface compared to glass bottles treated by the prior art method, in particular the wet scratch resistance was significantly enhanced.

[0143] Furthermore, label adhesion was excellent for the inventive examples and mostly better than the comparative examples (see especially the results shown in Table 2). It is also advantageous that bottle properties such as the optical appearance or the (basic) strength of the bottle were not compromised.

[0144] Other embodiments of the invention will be apparent to those skilled in the art from consideration of this specification or practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with the true scope of the invention being defined only by the following claims.

Claims

1. 1. A method for treating at least one glass surface, comprising: a) providing a substrate comprising said at least one glass surface; b) treating said at least one glass surface with a compound of formula (A): 【Chemical 1】 During the ceremony, Each R ａ１ are independently selected from the group consisting of hydrogen, alkyl groups, polyether groups, and aryl groups; Each R ａ２ are independently an alkanediyl group, R ａ３ is selected from the group consisting of hydrogen, alkyl groups, and aryl groups; m is an integer ranging from 0 to 3; n is an integer ranging from 0 to 3 with a silane formulation comprising at least one bis-silyl compound comprising at least one building block according to c) treating the at least one glass surface with an additional formulation comprising at least one lubricant selected from the group consisting of waxes, fatty acids and fatty acid esters, so as to obtain at least one treated glass surface. A method comprising:

2. The bis-silyl compound is represented by the formula (B) 【Chemistry 2】 During the ceremony, Each R ｂ１ are independently selected from the group consisting of hydrogen, alkyl groups, and aryl groups; R ｂ２ is an alkyl group, R ｂ３ is an alkanediyl group, R ｂ４ is selected from the group consisting of hydrogen, alkyl groups, aryl groups, and alkaryl groups; Each R ｂ５ are independently an alkanediyl group, R ｂ６ is selected from the group consisting of hydrogen, alkyl groups, aryl groups, and alkaryl groups; R ｂ７ is selected from the group consisting of hydrogen and alkyl groups; b is selected from 0 and 1; c is selected from 0, 1 and 2; d is selected from 0, 1 and 2; However, the sum of b and c is in the range of 0 to 2.

2. The method of claim 1, comprising at least one building block according to claim 1.

3. 3. The method of claim 1, wherein the silane formulation comprises at least one acid.

4. 4. The method of claim 1, wherein the silane formulation comprises water.

5. 5. The method according to claim 2, wherein the numerical ratio of the at least one building block according to formula (A) to the at least one building block according to formula (B) in the bis-silyl compound is 1 to 1 to 250.

6. 6. The method according to any one of claims 1 to 5, characterized in that the method does not use any tin compounds.

7. R ａ１ is selected from the group consisting of hydrogen and C1-C4 alkyl groups, and R ａ２ is a C2-C4-alkanediyl group, and R ａ３ 7. The process according to claim 1, wherein is selected from the group consisting of hydrogen and C1-C4-alkyl groups.

8. 8. The method according to any one of claims 1 to 7, characterized in that the amount of the at least one bis-silyl compound in the silane formulation is in the range of 0.001 to 10 wt.-%, preferably 0.01 to 4 wt.-%, more preferably 0.05 to 1 wt.-%, even more preferably 0.1 to 0.8 wt.-%, based on the total silane formulation.

9. 9. The method according to any one of claims 1 to 8, characterized in that the at least one lubricant is a wax, preferably selected from the group consisting of amide waxes, polyolefin waxes and copolymers of polyolefin waxes, more preferably the at least one lubricant is a polyolefin wax or a copolymer thereof, even more preferably a polyolefin wax, and even more preferably a polyethylene wax.

10. The silane formulation is a compound represented by formula (I) 【Chemistry 3】 During the ceremony, Each R ｙ１ are independently selected from the group consisting of hydrogen, alkyl groups, polyether groups, and aryl groups; R ｙ２ is an alkyl group, R ｙ３ is an alkanediyl group, R ｙ４ is selected from the group consisting of hydrogen, alkyl groups, aryl groups, and alkaryl groups; Each R ｙ５ are independently an alkanediyl group, R ｙ６ is selected from the group consisting of hydrogen, alkyl groups, aryl groups, and alkaryl groups; R ｙ７ is selected from the group consisting of hydrogen and alkyl groups; f is selected from 0, 1 and 2; g is selected from 0 and 1; h is selected from 0, 1 and 2; However, the sum of f and g is preferably in the range of 0 to 2.

10. The method according to claim 1, further comprising the step of: providing at least one silane-based compound comprising at least one building block according to claim 1.

11. 1. A composition comprising a compound of formula (A) as an adhesion promoter for at least one lubricant selected from the group consisting of waxes, fatty acids and fatty acid esters on a glass surface of a substrate 【Chemistry 4】 During the ceremony, Each R ａ１ are independently selected from the group consisting of hydrogen, alkyl groups, and aryl groups; Each R ａ２ are independently an alkanediyl group, R ａ３ is selected from the group consisting of hydrogen, alkyl groups, and aryl groups; m is an integer ranging from 0 to 3; n is an integer ranging from 0 to 3 2. Use of a silane formulation comprising at least one bis-silyl compound containing at least one building block according to claim 1.

12. i) at least one glass surface; ii) at least one silane-based layer obtained by treating said at least one glass surface with a silane formulation according to claims 1 to 10; iii) at least one additional layer on said silane-based layer comprising at least one lubricant selected from the group consisting of waxes, fatty acids and fatty acid esters. A substrate comprising:

13. 13. The substrate according to claim 12, characterized in that the substrate is a hollow container, preferably selected from the group consisting of bottles, thermoses, ampoules, tubes, jars, vials and flasks.

14. 14. Use of a hollow container according to claim 13 for storing therein a fluid or a solid, preferably a fluid, more preferably a liquid, even more preferably a beverage.

15. P1) Formula (A) 【Chemistry 5】 During the ceremony, Each R ａ１ are independently selected from the group consisting of hydrogen, alkyl groups, and aryl groups; Each R ａ２ are independently an alkanediyl group, R ａ３ is selected from the group consisting of hydrogen, alkyl groups, and aryl groups; m is an integer ranging from 0 to 3; n is an integer ranging from 0 to 3 a presilane formulation comprising at least one bis-silyl compound containing at least one building block according to P2) A pre-addition formulation comprising at least one lubricant selected from the group consisting of waxes, fatty acids and fatty acid esters. Kit of parts including.

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