Compositions and methods for treating glass surfaces

Abstract

The present invention relates to a composition and a method for treating at least one glass surface, preferably the surface of a glass container such as a glass bottle. The present invention further relates to a substrate comprising at least one layer obtained by treating its at least one glass surface with a composition according to the present invention.

Description

[Technical Field]

[0001] The present invention relates to a composition and a method for treating at least one glass surface, preferably the surface of a glass container such as a glass bottle. The present invention further relates to a substrate comprising at least one layer obtained by treating its at least one glass surface with a composition according to the present invention.

[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. Australian Patent No. 715826 (Application No. AU199731796) teaches the use of lubricants such as monoaminosilanes and polyolefins on glassware to impart a certain degree of abrasion resistance to the surface.

[0005] US Patent No. 6,096,394 discloses the use of organopolysiloxanes in cold end coatings for glassware.

[0006] 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.

[0007] However, to date, prior art coatings using silanes or compounds derived therefrom lack scratch resistance (i.e., dry scratch resistance 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.

[0008] 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 composition and method that allows for a sufficiently high scratch resistance of the treated glass surface without the use of ecologically harmful tin compounds.

[0009] 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.

[0010] Summary of the Invention These objectives are: a) 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 At least one bis-silyl compound comprising at least one building block according to b) at least one lubricant selected from the group consisting of waxes, fatty acids, and fatty acid esters; The problem is solved by a composition for treating at least one glass surface, comprising:

[0011] Surprisingly, the compositions according to the present invention are extremely stable. They can be used and stored for a period long enough for industrial use. Stability in the context of the present invention is primarily understood to mean that the compositions can be used for the purposes of the present invention, i.e., for coating substrates, particularly glass surfaces. The compositions according to the present invention preferably do not exhibit precipitation or the like. The minimum period is 24 hours (at 20°C). Preferably, the period is at least one week (at 20°C) or ideally at least one month (at 20°C).

[0012] Advantageously, the compositions according to the invention are ecologically friendly, since tin compounds are no longer required.

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

[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% or wt%) unless otherwise specified. Yields are given as a percentage of the theoretical yield. Concentrations given herein refer to the mass of the entire solution, dispersion, or composition unless otherwise specified. Room temperature means 20°C.

[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 composition according to the present invention comprises: a) at least one bis-silyl compound comprising at least one building block according to formula (A) (which compound is hereinafter referred to as "bis-silyl compound"), b) at least one lubricant selected from the group consisting of waxes, fatty acids, and fatty acid esters; Includes.

[0024] Bis-silyl compounds are known in the art and are commercially available, or can be prepared by known methods. For example, oligomeric or polymeric bis-silyl compounds 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.

[0025] 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.

[0026] 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.

[0027] 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 a3 is 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. a1is 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.

[0028] m is preferably selected from 0, 1 and 2. n is preferably selected from 0, 1 and 2. More preferably, m and n are selected from 0, 1 and 2. Preferably, at least one of m and n is less than 3, more preferably, m and n are (both) less than 3.

[0029] 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, Each 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)).

[0030] The additional building blocks according to formula (B) in the bis-silyl compound advantageously further improve the wet scratch resistance of the glass surface treated with the composition and further prevent the occurrence of optical degradation of the treated glass surface.

[0031] 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.

[0032] 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. b3 is preferably a C1-C8 alkanediyl group, more preferably a C2-C4 alkanediyl group, and even more preferably 1,3-propanediyl. 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. 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. b7 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 b7 is even more preferably hydrogen. b4 , R b6 and R b7It is even more preferred that b is hydrogen. b is preferably 0. c is preferably selected from 0 and 1. d is preferably 0.

[0033] 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.

[0034] 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 (B and B1) 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).

[0035] 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.

[0036] 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.

[0037] 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, still more preferably 1 to 1-10, resulting in optimal wet scratch resistance of glass treated with a composition according to the invention comprising such bis-silyl compound.

[0038] 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).

[0039] Preferably, at least one bis-silyl compound is an oligomer or polymer. For this purpose, at least one of m and n is selected from 0, 1 and 2. When at least one bis-silyl compound is an oligomer or polymer, an improved crosslink density can be obtained for the film obtained from the bis-silyl compound. The improved crosslink density leads to improved dry and wet scratch resistance of the treated surface. The oligomer according to the present invention comprises (in total) 2 to 4 building blocks according to formula (A) and (optionally) (B), and the polymer comprises (in total) at least 5 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]

[0040] The 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.

[0041] When the 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 the bis-silyl compound contains two or more building blocks according to formula (A) and optionally (B), they are typically arranged by bonding oxygen atoms (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').

[0042] 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.

[0043] An alternative representation of the building blocks described in formula (A) is as follows: [ka]

[0044] This alternative representation of the building block according to formula (A) is similar to the "O" in other representations of the building block according to formula (A). (3-m / 2) " and "O (3-n / 2) " emphasizes the bridging function of the oxygen atoms bonded to the silicon atoms, generally shown as ". The free valences of these oxygen atoms (shown as bonds to wavy lines) can be filled with any suitable partner, preferably with silicon atoms of other building blocks according to formula (A) and / 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.

[0045] Similarly, an alternative representation of the building block according to formula (B) can be written as follows: [ka]

[0046] 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]

[0047] As previously described herein, 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. By the 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.

[0048] Preferably, the amount of at least one bis-silyl compound in the composition is in the range of 0.001 to 10% by weight, preferably 0.01 to 4% by weight, more preferably 0.05 to 1% by weight, and even more preferably 0.1 to 0.8% by weight, based on the total composition. If more than one bis-silyl compound is included in the composition, the amount of all bis-silyl compounds is preferably in the range defined above.

[0049] The composition of the present invention comprises at least one lubricant. The at least one lubricant is selected from the group consisting of waxes, fatty acids, and fatty acid esters. Preferably, the at least one lubricant is a wax, more preferably, the at least one lubricant is selected from the group consisting of amide waxes, polyolefin waxes, and copolymers thereof, even more preferably, the at least one lubricant is selected from the group consisting of polyolefin waxes and copolymers thereof, even more preferably, the at least one lubricant is a polyolefin wax, and even more preferably, the at least one lubricant is a polyethylene wax. The preferences outlined above allow for increased scratch resistance and improved stability of the composition of the present invention. Furthermore, when used as the at least one lubricant, fatty acids and fatty acid esters do not provide the same long-lasting effect as waxes.

[0050] The waxes are preferably selected from natural and synthetic waxes, including modern waxes such as beeswax, carnauba wax or candelilla wax, fossil waxes such as montan wax or its derivatives, and petroleum waxes (both paraffin wax and microcrystalline wax).

[0051] 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.

[0052] Non-polar waxes such as petroleum waxes, Fischer-Tropsch waxes and polyolefin waxes such as polyethylene waxes are preferably used in their oxidized form for better dispersibility. Such oxidized waxes have been known for some time and can be prepared by standard means.

[0053] 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 the composition of the present invention with improved stability and enhanced scratch resistance.

[0054] The melting point of the polyethylene wax is preferably in the range of 50 to 170°C, more preferably 80 to 150°C, and even more preferably 100 to 135°C, as measured in accordance with DIN 51532 (2012). This range provides the composition of the present invention with improved stability and enhanced scratch resistance.

[0055] The polyethylene optionally has 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.

[0056] 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.

[0057] To improve the dispersibility of polyethylene wax and thereby the stability of the composition according to the invention, it is advantageous to use a copolymer of polyethylene wax containing 50 mol% or more ethylene and 50 mol% or less polar monomer, such as an ethylene-vinyl acetate copolymer wax or a copolymer of ethylene and acrylic acid. Another possible method for preparing dispersible polyethylene is to graft an unsaturated polar monomer, such as maleic anhydride, onto polyethylene in the melt. For this purpose, it is generally useful to add a free-radical initiator. The polyethylene modified in this way can be easily converted into a nonionic, anionic, or cationic dispersion by conventional methods, if desired, after further modification, usually with the addition of one or more emulsifiers (also known in the art as "surfactants"; see below).

[0058] The polyethylene wax is preferably selected from the group consisting of unmodified polyethylene waxes, copolymers of polyethylene, and polyethylene grafted with at least one polar monomer. More preferably, the polyethylene wax is selected from the group consisting of copolymers of polyethylene and polyethylene grafted with at least one polar monomer. These preferred polyethylene waxes are preferably used in their oxidized form as described hereinabove.

[0059] 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.

[0060] 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.

[0061] 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 any other combination can be used as at least one lubricant.

[0062] The amount of at least one lubricant in the composition is preferably 0.01 or 0.05 to 5% by weight, more preferably 0.1 to 2% by weight, based on the composition. If two or more lubricants are used in the composition, the total amount of all lubricants is preferably in the above range.

[0063] The composition according to the invention comprises, in addition to at least one bis-silyl compound, a 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 y4is 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.The silane-based compound preferably does not comprise a building block according to formula (A). 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.

[0065] 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 y7is 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.

[0066] 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.

[0067] In the composition of the present invention, the amount of the silane compound is preferably in the range of 0.001 to 20% by weight, more preferably 0.01 to 8% by weight, even more preferably 0.05 to 2% by weight, and even more preferably 0.1 to 1.6% by weight, based on the total composition.

[0068] 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).

[0069] 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.

[0070] The weight ratio of the at least one silane-based compound to the at least one bis-silyl compound, when the first-mentioned compound is present in the composition 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.

[0071] The composition according to the present invention preferably comprises water in an amount of preferably 1 to 99.99 wt. %, more preferably 10 to 99.9 wt. %, even more preferably 50 to 99.7 wt. %, and even more preferably 90 to 99.6 wt. %, based on the total composition.

[0072] The compositions of the present invention preferably include at least one acid, which further enhances the stability of the composition. The acid typically has a pK sufficiently high to transfer a proton onto another component in the composition. 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.

[0073] 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.

[0074] The amount of the at least one acid may be based, inter alia, on the amine value of the at least one bis-silyl compound (and, if present, the amine value of the at least one silane-based compound). Preferably, the amount of the at least one acid ranges from 0.00001 to 10% by weight, more preferably from 0.01 to 1% by weight, and even more preferably from 0.2 to 0.1% by weight, based on the total composition.

[0075] The pH value of the composition of the present invention is typically in the range of 1 to 14. The pH value of the composition of the present invention is likely to be in the range of 1 to 7, more preferably 3.5 to 6.8, and even more preferably 4.5 to 6.5. This pH range advantageously improves the stability of the composition of the present invention. The preferred pH range avoids potential glass corrosion when the substrate to be treated has a glass surface; it has been found that if the composition has a pH value greater than 7, scratch resistance may, in some cases, be degraded.

[0076] The composition optionally includes at least one organic solvent. Any organic solvent suitable for dissolving or dispersing the components of the composition can be used. The at least one organic solvent is preferably a polar solvent, more preferably an alkanol, even more preferably a C1-C4-alkanol such as methanol or ethanol. When present in the composition of the present invention, 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, even more preferably 1.0% by weight or less, and even more preferably 0.25% by weight or less, based on the total composition. Ideally, the amount is less than 0.1% by weight, further improving the ecological effectiveness of the present invention. In particular (for ecological and safety reasons), the amount of alkanol in the composition of the present invention is preferably 1% by weight or less, preferably 0.25% by weight or less, and ideally 0.1% by weight or less, based on the total composition of the present invention.

[0077] Composition is preferably dispersion.Dispersion in the context of the present invention is preferably emulsion or suspension.Dispersion is preferably emulsion, which facilitates the treatment of at least one glass surface with composition, especially when composition is applied by spraying, by avoiding the nozzle of spray application device from clogging.

[0078] In general, especially when the composition is a dispersion (e.g., emulsion), the composition of the present invention 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 composition of the present invention in an amount of 0.01 to 10 wt. %, more preferably 0.1 to 2.5 wt. %, and even more preferably 0.2 to 1.0 wt. % based on the total composition of the present invention. 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.

[0079] 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.

[0080] 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

[0081] 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.

[0082] Preferably, the anionic emulsifier is of formula (L) [ka] During the ceremony, R L 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. is expressed by

[0083] 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. Anionic emulsifiers are less preferred because the preferred pH range of the composition according to the invention defined above can cause the anionic emulsifier to lose its water solubility, thus resulting in a less stable composition.

[0084] 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.

[0085] Preferably, the composition according to the present invention comprises 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 composition (and the solid 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 The value can be measured by dynamic light scattering, preferably using a Malvern Panalytical according to ISO 22412:2017-02. Colloidal silica can improve the stability of the compositions according to the present invention.

[0086] Optionally, the composition of the present invention 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. The organic polymer improves the adhesion of labels, paints, or inks applied to the surface after applying the composition of the present invention.

[0087] The solid content of the composition according to the present invention is preferably in the range of 0.01 to 15%, more preferably 0.05 to 10%, and even more preferably 0.1 to 1%.

[0088] In one embodiment of the present invention, the composition according to the present invention comprises: I) at least one bis-silyl compound; II) at least one lubricant; III) at least one emulsifier; IV) preferably at least one acid and V) water Contains (or consists of)

[0089] The specified ingredients are preferably included in compositions according to the present invention in the amounts set forth above.

[0090] In a further embodiment of the present invention, the composition according to the present invention comprises: I) at least one bis-silyl compound; II) at least one lubricant; III) at least one emulsifier; IV) preferably at least one acid; V) Water and VI) at least one silane-based compound Contains (or consists of)

[0091] The specified ingredients are preferably included in compositions according to the present invention in the amounts set forth above.

[0092] Preferably, the composition of the present invention does not contain polyisocyanates in an amount of 0.1% by weight or more. More preferably, the composition of the present invention does not contain polyisocyanates. Polyisocyanates adversely affect the stability of the composition of the present invention. Polyisocyanates in the context of the present invention are compounds having at least two isocyanate groups (either free or blocked, e.g., oxime-blocked). Such polyisocyanates are described, inter alia, in U.S. Pat. No. 6,403,175 (column 8, line 1 - column 9, line 7).

[0093] The compositions of the present invention 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. The present invention further relates to a method for preparing the compositions of the present invention, which comprises mixing at least one bis-silyl compound, at least one lubricant, and optionally at least one emulsifier, optionally at least one acid, and optionally water (and optionally the aforementioned additional optional components described herein) in a suitable container to provide the compositions of the present invention.

[0094] Within the scope of the present invention, it is also possible to prepare the bis-silyl compounds as described in US Patent Application Publication No. 2011 / 02688911 (see in particular paragraphs 17-174 and Examples 1-41 thereof) and add any possible further ingredients before, during or after their preparation, thereby obtaining a composition. It is preferable to disperse the at least one lubricant before adding it to the at least one bis-silyl compound.

[0095] In another aspect, the present invention relates to a kit of parts for preparing a composition according to the present invention, said kit of parts comprising Part A and Part B, wherein Part A comprises at least one bis-silyl compound and Part B comprises at least one lubricant. The composition according to the present invention can be easily prepared by mixing Part A and Part B of the kit of parts according to the present invention. Mixing Part A and Part B can be achieved by using standard means (see above). The composition thus obtained can be optionally diluted with water and, optionally, at least one solvent. For the reasons stated above, water (alone) is preferred.

[0096] Part A preferably comprises water. Part A optionally comprises at least one solvent (if present). Part A of the kit-of-parts according to the invention preferably comprises at least one acid.

[0097] Part B preferably comprises water. Part B of the kit-of-parts according to the invention preferably comprises at least one emulsifier.

[0098] The kit of parts according to the present invention preferably comprises: Part A comprising at least one bis-silyl compound, water, and at least one acid; and Part B, which comprises at least one lubricant, water, and at least one emulsifier. Includes.

[0099] More preferably, the kit of parts according to the present invention comprises: Part A comprising at least one bis-silyl compound, at least one silane-based compound, water, and at least one acid; and Part B, which comprises at least one lubricant, water, and at least one emulsifier. Contains (or consists of)

[0100] As can be expected, the concentrations of the components in parts A and B of the kit-of-parts of the present invention may deviate from the concentrations described for the composition of the present invention.

[0101] The kit-of-parts of the present invention offer two advantages: they have an extremely long shelf life and can be stored for long periods even at high temperatures, such as 40°C. Also, the kit-of-parts allows for a simple method of preparing the compositions of the present invention, without requiring special equipment.

[0102] The present invention further provides a method for treating at least one glass surface of a substrate, comprising the steps of: To obtain a treated glass surface, a) providing a substrate comprising at least one glass surface; and b) treating said at least one glass surface with a composition according to the invention The present invention relates to a method, including the method of

[0103] The method of the present invention comprises method steps a) and b), which are carried out in a predetermined order. The method of the present invention optionally comprises further method steps carried out before, after and / or between said method steps.

[0104] In step a) of the method of the present invention, a substrate having at least one glass surface is prepared. The substrate is not particularly limited in its form or function, as long as it has at least one glass surface. Preferably, the substrate is entirely made of glass. In one embodiment of the present invention, the substrate consists of at least one glass surface.

[0105] 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.

[0106] 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.

[0107] Optionally, the method comprises after method step a) and before method step b) the further method step: ai) cleaning at least one glass surface.

[0108] 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.

[0109] In method step b) of the method according to the invention, at least one glass surface is treated with the composition according to the invention, either completely or only in one or more parts thereof.

[0110] 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.

[0111] Optionally, the temperature of the composition is adjusted to a value in the range of 10 to 80°C, preferably 20 to 30°C, before the composition is used to treat at least one glass surface with the composition.

[0112] Generally, it is desirable to maintain the temperature difference between the composition and the glass surface within a certain range. For example, a temperature difference of 100°C or more between the composition and the glass surface should be avoided. Otherwise, the glass surface may be damaged. The acceptable temperature difference depends on the type of glass used. Those skilled in the art are aware of this and can select an appropriate temperature based on general knowledge or routine experimentation.

[0113] At least one glass surface is treated with the composition by conventional means. Preferably, the treatment of at least one glass surface in method step b) is carried out by spraying, dipping, rolling, painting, and combinations thereof. Spraying is particularly preferred.

[0114] 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. To this end, the composition preferably does not contain (intentionally added) tin compounds. This means that the content of tin compounds in the composition of the present invention 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 composition is 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.

[0115] In yet another aspect, the present invention further comprises: i) at least one glass surface; and ii) at least one layer obtained by treating at least one glass surface with the composition according to the invention (hereinafter referred to as "layer ii"); The present invention relates to a substrate comprising:

[0116] Layer ii) is obtained by treating at least one glass surface with the composition according to the present invention. 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). The substrate optionally comprises one or more additional layers located below or above layer ii), with the optional additional layers preferably being located on layer ii). Layer ii) is preferably disposed directly on at least one glass surface. Layer ii) may be present over the entire glass surface or only over one or more portions thereof. Optionally, the substrate comprises one or more adhesive layers on layer ii). Conventional adhesives may be used for this purpose without limitation. A label is optionally disposed on the optional adhesive layer. The label is typically made of paper or the like. For decorative or informational purposes, the label may be printed on the side facing away from the glass surface.

[0117] 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.

[0118] In one preferred embodiment of the present invention, the substrate is selected from the group consisting of bottles, thermoses, ampoules, tubes, jars, vials and flasks and comprises at least one glass surface, a layer ii) on the at least one glass surface, an adhesive layer on layer ii) and a label on the adhesive layer.

[0119] 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.

[0120] The invention will now be described by reference to the following non-limiting examples.

[0121] 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.

[0122] Untreated 1 L soda-lime silicate glass bottles were used as glass substrates in all experiments. A spray gun (IPOTOOLS Mini HLVP Spray Gun) was used as a manual applicator.

[0123] In the following experiments, the following products were used as lubricants: [Table 1]

[0124] All lubricants were aqueous dispersions of oxidized or partially oxidized polyethylene.

[0125] 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, holding one bottle in each hand. The test was repeated several times by at least two people in different areas on the glass bottles. 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 rinse water. The pressure and scratch time (15 seconds) were kept constant. Ranking: No scratches: 1, slight scratches: 2, scratches across the entire test surface: 3

[0126] 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).

[0127] 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.

[0128] 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.

[0129] Calculation:

number

[0130] Determination of the free alcohol content in the composition 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).

[0131] The pH value was determined according to DIN EN ISO 10523 (2012). The viscosity was measured according to DIN 53015 (2019).

[0132] Preparation example Comparative Preparation 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

[0133] Comparative Preparation 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

[0134] Comparative Preparation 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 wt% Viscosity: 3mPas pH: 11.2

[0135] Preparation Example 1: Preparation of bis-silyl compound 1 A reactor was charged with 300 g of deionized (DI) water and 5.8 g of an aqueous solution of formic acid (85 wt%) and heated to 65 °C. 45 g of bis[3-(triethoxysilyl)propyl]amine was added to the solution within 30 min. The reaction mixture was stirred at 65 °C for 3 h until the silane was completely hydrolyzed. If necessary, the pH was adjusted to about 4.3 using formic acid (using the aqueous formic acid solution described above). Then, about 60 g of ethanol / water was removed under reduced pressure (130-200 mbar). If necessary, the resulting solution was diluted with DI water to obtain 300 g of solution. The resulting solution containing the bis-silyl compound formed a clear, yellowish liquid and had the following analytical and physical data: Solid content: 8.9% by weight Free ethanol content: 1.6% by weight Amine content as NH2: 0.48% pH: 4.3

[0136] Preparation Example 2: Preparation of Silane Compound 1 A four-neck flask equipped with a stirrer, a dropping funnel, and a distillation column with a bridge was charged with 340.2 g of DI water under a nitrogen atmosphere. After heating the water to 40°C, 340.0 g of 3-aminopropyltriethoxysilane was slowly added. The temperature of the reaction mixture rose to approximately 63°C. After complete addition of 3-aminopropyltriethoxysilane, the pressure was immediately reduced. Under a reduced pressure of 106 to 105 mbar, 371.9 g of ethanol / water (75% hydrolysis alcohol) was distilled off within 4.75 hours. After approximately 134.9 g had distilled off, a total of 78.3 g of DI water was added dropwise within 2.5 hours for dilution. The reaction mixture was colorless, transparent, and non-viscous during and toward the end of the distillation. No precipitate or sediment was present on the rim of the flask. After cooling, the system was purged with nitrogen. The yield was 389.7 g of a clear, colorless product. Solid content 44.7% by weight Free ethanol content 0.3% by weight

[0137] Mixture 1 (containing at least one bis-silyl compound and at least one silane-based compound): A reactor was charged with 192.81 g of DI water and 113.64 g of Preparation Example 2. The mixture was stirred, and 26.90 g of an aqueous solution of formic acid (85 wt %) was slowly added. Upon completion of the addition of formic acid, 666.66 g of Preparation Example 1 was added, and the resulting mixture was stirred for an additional 10 minutes.

[0138] Stability testing Mixture 1 was placed in a 200ml glass bottle equipped with a magnetic stir bar and diluted with the amount of deionized water shown below. 2.0g of lubricant was then added before shaking the bottle until the contents were homogenous. The bottle was stored at 20°C for one week and periodically inspected for appearance and stability. The results are shown in the table below. [Table 2]

[0139] The composition was sufficiently stable to be used for glass treatment purposes. (R) The composition containing RP40 was cloudy but still stable enough to be used to treat glass (entries D and H, see Application Examples).

[0140] Glass Processing Method The glass substrates were treated by spray coating using a manual applicator. For this purpose, the bottles were placed on a rotating tray and rotated twice while treating the entire surface of the bottle. Before the treatment described, the bottles were heated in an oven to the temperature given below. The spray conditions were as follows: Nozzle diameter: 0.8 mm Applicable pressure: 4.5 bar Spray distance: 20~30cm Spray amount: 20ml / min Rotation time: approx. 6-7 seconds Bottle temperature 120~124℃

[0141] Application Examples 1 to 4 (according to the present invention) A 200ml glass bottle equipped with a magnetic stir bar was charged with 2.5g of Mixture 1 and 195.5g of deionized water. 2.0g of lubricant was then added before shaking the bottle until homogeneous. The pH values ​​of the resulting compositions ranged from 6.0 to 6.5. The resulting compositions were used to treat glass bottles as described above after 0.5 and 24 hours of storage at room temperature, respectively. The results are shown in the table below. [Table 3]

[0142] Application Examples 5 to 8 (according to the present invention) A 200ml glass bottle equipped with a magnetic stir bar was charged with 5.0g of Mixture 1 and 193.0g of deionized water. 2.0g of lubricant was then added before shaking the bottle until homogenous. The pH value of the resulting composition ranged from 6.0 to 6.5. The resulting composition was then used to treat glass bottles after 0.5 hours of storage at room temperature. The results are shown in the table below. [Table 4]

[0143] Comparative application example 1 (one-step approach) Prepare 98% by weight water and, with stirring, add aminopropyltriethoxysilane (AMEO) at the concentrations given in the table below and 1% by weight Glasskote. (R) An application mixture was prepared by adding SC100. The application mixture thus obtained was used to treat glass bottles. The results are shown in the table below. [Table 5]

[0144] Both dry and wet scratch resistance was inferior to that obtained with the composition according to the invention.

[0145] Comparative application example 2 (two-stage approach) A solution of each of Comparative Preparations 1-3 was prepared by diluting it with water to the concentration given in the table below (column headed "Amount of Silane Oligomer in Spray Solution [wt %]"). A dilution of lubricant was used (1 g of Glasskote diluted with 99 g of water). (R) The bottles were first treated with the spray solution of the comparative formulation and then with a dilution of the lubricant. The results are shown in the table below. [Table 6]

[0146] The results of the application examples clearly show that the compositions of the present invention improve the scratch resistance of glass surfaces treated with the compositions of the present invention compared to glass bottles treated by prior art methods. In particular, wet scratch resistance was significantly enhanced. Surprisingly, some compositions (#1 and #2) showed enhanced results when stored for longer periods of time.

[0147] Furthermore, label adhesion was excellent for the inventive examples and mostly better than the comparative examples (see results shown in Table 2). It is also beneficial that bottle properties such as the optical appearance or (basic) strength of the bottle were not compromised.

[0148] 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 composition for treating at least one glass surface, comprising: a) 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 At least one bis-silyl compound comprising at least one building block according to b) at least one lubricant selected from the group consisting of waxes, fatty acids, and fatty acid esters; A composition comprising:

2. 2. The composition according to claim 1, characterized in that the amount of said at least one bis-silyl compound in said composition ranges from 0.001 to 10% by weight, preferably from 0.01 to 4% by weight, more preferably from 0.05 to 1% by weight, even more preferably from 0.1 to 0.8% by weight, based on the total composition.

3. 3. The composition according to claim 1, wherein said at least one bis-silyl compound is an oligomer or a polymer.

4. 4. The composition according to claim 1, wherein the at least one lubricant is a wax, preferably selected from the group consisting of amide waxes, polyolefin waxes and copolymers thereof, more preferably selected from the group consisting of polyolefin waxes and copolymers thereof, even more preferably a polyolefin wax.

5. 5. The composition of claim 4, wherein said at least one lubricant is a polyethylene wax.

6. 6. Composition according to any one of claims 1 to 5, characterized in that the amount of said at least one lubricant ranges from 0.01 to 5% by weight, preferably from 0.1 to 2% by weight, based on the composition.

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 composition according to claim 1, wherein is selected from the group consisting of hydrogen and C1-C4-alkyl groups.

8. 8. The composition according to claim 1, wherein the composition comprises water.

9. The composition comprises a compound represented by formula (I): 【Chemistry 2】 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 and 1; g is selected from 0, 1 and 2; h is selected from 0, 1 and 2; However, the sum of f and g is preferably in the range of 0 to 2.

9. The composition according to claim 1, comprising at least one silane-based compound containing at least one building block according to

10. 10. The composition according to any one of claims 1 to 9, characterized in that the pH value of the composition according to the invention is in the range from 1 to 7, preferably from 3.5 to 6.8, more preferably from 4.5 to 6.

5.

11. The composition comprises: I) said at least one bis-silyl compound; II) said at least one lubricant; III) said at least one emulsifier; IV) optionally at least one acid, and V) water 11. A composition according to any one of claims 1 to 10, characterized in that it comprises or consists of:

12. R ａ３ 12. The composition according to claim 1, wherein is hydrogen.

13. 13. A kit of parts for preparing the composition of any one of claims 1 to 12, comprising Part A and Part B, wherein Part A comprises said at least one bis-silyl compound and Part B comprises said at least one lubricant.

14. 13. A method of preparing a composition according to any one of claims 1 to 12, comprising mixing in a suitable container the at least one bis-silyl compound, the at least one lubricant, and optionally the at least one emulsifier, optionally the at least one acid, and optionally water to provide the composition according to any one of claims 1 to 12.

15. 1. A method for treating at least one glass surface of a substrate, comprising: To obtain a treated glass surface, a) providing said substrate comprising said at least one glass surface; and b) treating said at least one glass surface with a composition according to any one of claims 1 to 12. A method comprising:

16. i) at least one glass surface; and ii) at least one layer obtained by treating said at least one glass surface with a composition according to any one of claims 1 to 12. A substrate comprising:

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