Compositions and methods for treating glass surfaces

Abstract

The present invention relates to compositions and methods for treating at least one glass surface, preferably the surface of a glass container such as a glass bottle. The invention also relates to a substrate comprising at least one layer obtained by treating at least one glass surface thereof with a composition according to the 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 also relates to a substrate comprising at least one layer obtained by treating at least one glass surface thereof with a composition according to the invention. Background Art

[0002] Glass obtains its strength and optical properties from a flawless surface, and any surface damage such as scratches or defects present on its surface significantly reduces its (basic) strength, in particular its compressive strength. In addition, the internal rupture strength (also known as internal pressure resistance) of glass containers such as bottles may be reduced due to surface damage. This poses a serious risk to anyone using such damaged bottles, in particular if they contain carbonated beverages, as such bottles may break. Such scratches and defects are usually caused by normal handling of the glass, for example when using or transporting glass bottles containing beverages. While a transparent and smooth glass surface is generally desired, surface damage to the glass - in particular when used for decorative purposes - is also an optical defect. Examples of products for which consumers generally cannot tolerate surface damage are mirrors, window panes and decorative glass objects.

[0003] In order to avoid the occurrence of scratches and the loss of strength, the glass is usually surface treated. This surface treatment protects the glass surface from surface damage. Typically, tin salts are applied to the glass surface at a temperature of about 500 ° C to form a thin tin oxide layer, followed by a layer containing a slip agent (also referred to as a lubricant in the art) such as a wax at a significantly lower temperature to reduce the wear of the glass surface by processing defects. Tin oxide is necessary to provide sufficient adhesion of the slip agent on the glass surface. Tin salts are generally ecologically problematic and harmful to humans. Therefore, organotin compounds are under regulatory pressure, and monobutyltin trichloride, one of the most commonly used tin compounds for coating glass bottles, will be phased out in Europe (CoRAP list ECHA) for this application. However, tin compounds are still in use because even if various alternatives are considered, the same protective properties are not achieved, so there is no acceptable alternative.

[0004] Various silanes and siloxanes have been proposed as alternatives to tin salts. These systems primarily use epoxy- and amino-functional silanes and siloxanes. AU715826B2 (application number AU199731796 B2) teaches the use of monoaminosilanes and slip agents such as polyolefins on glass articles to impart a certain degree of wear resistance to the surface.

[0005] US 6,096,394 B1 discloses the use of organopolysiloxanes in cold end coatings of glass articles.

[0006] JP 2004-196563 describes the use of a formulation containing a silane and a polymer dispersion. The silane is either monosilylsilane or (triethoxysilylpropyl)tetrasulfide. In the latter case, the odor of the sulfur silane is unacceptable for use on glass bottles, especially for applications containing beverages.

[0007] However, to date, prior art coatings using silanes or compounds derived therefrom lack scratch resistance (i.e., dry and wet scratch resistance), in particular wet scratch resistance. In addition, many silane-based systems suffer from poor stability of treatment solutions containing these compounds, requiring frequent replacement of such treatment solutions. This is environmentally and economically undesirable. Due to these drawbacks, they have not been introduced into industry, in particular not into large-scale applications.

[0008] Purpose of the invention

[0009] It is therefore an object of the present invention to overcome the disadvantages of the prior art.Another object of the present invention is to provide a composition and a method which allow a treated glass surface to have a sufficiently high scratch resistance without the use of ecologically harmful tin compounds.

[0010] It is of further interest that the optical appearance of the treated glass is not impaired, neither by the treatment itself nor by impairment caused by conventional handling. In addition, the adhesion of labels adhered to the treated glass surface must be acceptable. Summary of the invention

[0011] These objects are solved by a composition for treating at least one glass surface, comprising:

[0012] a) at least one bissilyl compound comprising at least one building block according to formula (A)

[0013]

[0014] in

[0015] Each R a1 are independently selected from hydrogen, alkyl, polyether and aryl groups,

[0016] Each R a2 are independently alkanediyl,

[0017] R a3 is selected from hydrogen, alkyl and aryl,

[0018] m is an integer from 0 to 3,

[0019] n is an integer from 0 to 3,

[0020] as well as

[0021] b) at least one slip agent selected from the group consisting of waxes, fatty acids and fatty acid esters.

[0022] Surprisingly, the composition according to the invention is very stable. It can be used and stored for a sufficiently long period of time to be ready for use in industry. Stability in the context of the present invention is primarily to be understood as meaning that the composition can be used for the purpose of the present invention, i.e. coating a substrate, in particular coating a glass surface. It preferably does not show any precipitate or the like. The minimum period of time is 24 h (at 20 ° C). Preferably the period of time is at least 1 week (at 20 ° C), or ideally at least 1 month (at 20 ° C).

[0023] Advantageously, the composition according to the invention is eco-friendly since no tin compounds are required.

[0024] The composition according to the invention advantageously reduces the number of scratches on at least one glass surface, thereby reducing the loss of (substantial) strength and internal pressure resistance during use and handling of substrates, in particular hollow containers such as bottles, treated with the composition according to the invention.

[0025] Preferred embodiments which achieve the above-mentioned objects particularly well are described in the following description and in the dependent claims. DETAILED DESCRIPTION OF THE INVENTION

[0027] Unless otherwise stated, the percentages in this specification are weight percentages (wt% or wt%). Yields are given as a percentage of theoretical yields. Unless otherwise stated, the concentrations given in this specification are based on the mass of the entire solution, dispersion or composition. Room temperature means 20°C.

[0028] According to the term "alkyl" of the present invention, side chain or non-branched alkyl containing cyclic and / or non-cyclic structural elements are included, wherein the cyclic structural element of alkyl naturally requires at least three carbon atoms. The C1-C18-alkyl in this specification and claims refers to an alkyl with 1 to X carbon atoms (X is an integer). C1-C18-alkyl, for example, includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, the tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, hexyl, heptyl and octyl, hexadecyl and octadecyl etc. Unless otherwise indicated below, alkyl is usually unsubstituted.

[0029] The term "alkane diyl" is a corresponding group with two free valences (bonding sites). Sometimes, it is referred to as "alkylidene" in the art. The residue according to the present invention comprises cyclic and / or non-cyclic structural elements, and can be straight and / or branched. C1-C4-alkane diyl, for example, includes 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, etc. Typically, unless otherwise specified below, alkane diyl is not substituted.

[0030] "Alkenyl" is an unsaturated alkyl group containing at least one olefinic (ie C=C-double) bond. The details and preferences described above for alkyl apply mutatis mutandis to alkenyl.

[0031] The term "aryl" according to the present invention refers to a cyclic aromatic hydrocarbon residue, such as phenyl or naphthyl. Unless otherwise stated below, an aryl group is generally unsubstituted.

[0032] The term "alkaryl" according to the present invention refers to a hydrocarbon group comprising at least one aryl group and at least one alkyl group, such as benzyl and p-tolyl. The bonding of such alkaryl to other moieties may occur via the alkyl or aryl group of the alkaryl. The above details and preferences for alkyl and aryl groups apply mutatis mutandis to the alkaryl group.

[0033] If more than one residue - be it an atom, a group of atoms or a whole building block - is selected from a given group, then, unless otherwise indicated below, each residue is selected independently of the others, which means that they may be selected as the same member or as different members of the group. for emphasis, as is customary in the art.

[0034] Unless technically infeasible or indicated otherwise, the embodiments and preferences described for one aspect of the invention apply mutatis mutandis to all other aspects thereof. Repetitions are omitted to improve the simplicity of the description.

[0035] The composition according to the invention comprises

[0036] a) at least one bis-silyl compound comprising at least one building block according to formula (A) (said compound will be referred to hereinafter as "bis-silyl compound")

[0037] as well as

[0038] b) at least one slip agent selected from the group consisting of waxes, fatty acids and fatty acid esters.

[0039] 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.

[0040] The polyether group is preferably -[CH 2 -CH(R')-O] j -R" group, wherein R' is selected from hydrogen and methyl, R" is selected from hydrogen, alkyl and aryl, and j is 1 or an integer of 3-100, more preferably 5-20.

[0041] R a1 is preferably selected from hydrogen and C1-C4-alkyl. More preferably, R a1 is hydrogen. a2 Preferably it is C1-C8-alkanediyl, more preferably C2-C4-alkanediyl, even more preferably 1,3-propanediyl. a3 is preferably selected from hydrogen and C1-C4-alkyl. More preferably, R a3 It's hydrogen.

[0042] R is particularly preferred a1 is selected from hydrogen and C1-C4-alkyl (more preferably each R a1 is hydrogen), R a2 is a C2-C4-alkanediyl group (each R a2 More preferably 1,3-propanediyl), R a3 is selected from hydrogen and C1-C4-alkyl (each R a3 More preferably, it is hydrogen. This particularly preferred selection of at least one building block according to formula (A) is referred to as a particularly preferred selection A1. Even more preferably, R a1 is hydrogen, R a2 is 1,3-propanediyl, R a3 is hydrogen. This particularly preferred selection of at least one building block according to formula (A) is referred to as a particularly preferred selection A2.

[0043] m is preferably selected from 0, 1 and 2, and 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 (both) are less than 3.

[0044] Preferably, the bis-silyl compound comprises (in addition to at least one building block according to formula (A)) at least one building block according to formula (B)

[0045]

[0046] in

[0047] Each R b1 are independently selected from hydrogen, alkyl and aryl,

[0048] R b2 is an alkyl group,

[0049] R b3 is an alkanediyl group,

[0050] R b4 is selected from hydrogen, alkyl, aryl and alkaryl,

[0051] Each R b5 are independently alkanediyl,

[0052] Each R b6 is selected from hydrogen, alkyl, aryl and alkaryl,

[0053] R b7 is selected from hydrogen and alkyl,

[0054] b is selected from 0 and 1,

[0055] c is selected from 0, 1 and 2,

[0056] d is selected from 0, 1 and 2,

[0057] The condition is that the sum of b and c is 0-2.

[0058] The additional structural unit according to formula (B) in the bis-silyl compound advantageously further improves the wet scratch resistance of the glass surface treated with the composition and further prevents the occurrence of optical degradation of the treated glass surface.

[0059] In case the bissilyl compound comprises at least one building block according to formula (B), at least one of m and n is less than 3.

[0060] Preferably, R b1 Preferably, R b1 is hydrogen. b2 Preferably, C1-C4-alkyl, R b2 More preferably, it is methyl. b3 Preferably it is C1-C8-alkanediyl, more preferably C2-C4-alkanediyl, even more preferably 1,3-propanediyl. b4 is preferably selected from hydrogen, alkyl and aryl, more preferably selected from hydrogen and C1-C4-alkyl, R b4 Even more preferably is hydrogen. Preferably, R b5 is C1-C8-alkanediyl, more preferably C2-C4-alkanediyl, even more preferably 1,2-alkanediyl. b6is preferably selected from hydrogen, alkyl and aryl, more preferably selected from hydrogen and C1-C4-alkyl, R b6 Even more preferably is hydrogen. b7 is preferably selected from hydrogen, alkyl and aryl, more preferably selected from hydrogen and C1-C4-alkyl, R b7 Even more preferably is hydrogen. Still even more preferably R b4 , R b6 and R b7 is hydrogen. b is preferably 0. c is preferably selected from 0 and 1. d is preferably 0.

[0061] A particularly preferred embodiment of the at least one building block according to formula (B) is a building block according to formula (B1):

[0062]

[0063] in

[0064] Each R b11 are independently selected from hydrogen and C1-C4-alkyl,

[0065] R b13 is C2-C4-alkanediyl, even more preferably 1,3-propanediyl,

[0066] R b14 is selected from hydrogen and C1-C4-alkyl, R b14 Even more preferably hydrogen,

[0067] R b17 is selected from hydrogen and C1-C4-alkyl, R b17 Even more preferably is hydrogen, and

[0068] c' is selected from 0, 1 and 2. Preferably all R b11 , R b14 and R b17 For hydrogen.

[0069] The building block according to formula (B1) is a preferred alternative to the aforementioned building block according to formula (B). Preferably, it is used as the sole alternative to the latter, or (less preferably) the two building blocks (B and B1) are used in combination. Preferably, the at least one bis-silyl compound comprises (or consists of) at least one building block using the aforementioned particularly preferred option A1 according to formula (A) and at least one building block according to formula (B1), because very good results can be obtained. More preferably, the at least one bis-silyl compound comprises (or consists of) at least one building block using the aforementioned particularly preferred option A2 according to formula (A) and at least one building block according to formula (B1), because the best results can be obtained.

[0070] The total number of structural units according to formula (A) and, if present, structural units according to formula (B) in the bisilazane 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.

[0071] The number or ratio of the structural units can be determined by standard means, such as 1 H, 13 C and / or 29 Si-NMR spectroscopy. Other suitable methods are known to those skilled in the art, such as gel permeation chromatography.

[0072] Preferably, the numerical ratio of the structural units according to formula (A) to the structural units according to formula (B) in the bisilazane compound is in the range of 1 (structural units according to formula (A)) to 0.1 - 1000 (structural units 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, resulting in optimal wet scratch resistance of the glass treated with the composition comprising such a bisilazane compound according to the invention.

[0073] At least one structural unit according to formula (A) and - if comprised in the bisilazane compound - at least one structural unit according to formula (B) preferably account for at least 50 wt%, more preferably 75 wt%, and even more preferably 90 wt% of the bisilazane compound. The bisilazane compound most preferably consists of one or more structural units according to formula (A) and optionally one or more structural units according to formula (B).

[0074] Preferably, the at least one bisilazane compound is an oligomer or a polymer. For this purpose, at least one of m and n is selected from 0, 1, and 2. If the at least one bisilazane compound is an oligomer or a polymer, an improved crosslink density of the film obtained from the bisilazane compound can be obtained. The improved crosslink density results in enhanced dry and wet scratch resistance of the treated surface. The oligomers according to the invention comprise (in total) 2 to 4 structural units according to formula (A) and (optionally present) structural units of (B), and the polymers according to the invention comprise (in total) at least 5 structural units according to formula (A) and (optionally present) structural units of (B). Non-limiting examples of oligomers comprising one structural unit of (A) and (B) are described below:

[0075]

[0076] Oligomers and polymers generally contain one or more linear, branched and cyclic structures formed from building blocks according to formula (A) and / or (B). If the bissilyl compound contains more than one building block according to formula (A) and optionally (B), the building blocks described herein may also be understood as structural repeating units.

[0077] If the at least one bis-silyl compound is an oligomer or a 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. If the bis-silyl compound contains more than one building block according to formula (A) and optionally (B), they are usually bonded to each other via a connecting oxygen atom between the silicon atoms of the corresponding building blocks (depicted in the chemical formula as O y / 2 , where y represents one of (3-m), (3-n), (3-bc) or (3-c')).

[0078] As commonly used in the art, R g -SiO (4-g / 2) It is understood that the depicted silicon atom carries 4-g oxygen atoms (g is an integer from 0 to 4) and g residues R. The oxygen atom is bound to the silicon atom by a single bond and therefore has another substituent, such as the above-mentioned single (unity) silicon atom. In the case of the present invention, the other silicon atom is preferably one of the building blocks according to formula (A) or (B). If g is 3, there is an M unit. If g is 2, there is a D unit. If g is 1, there is a T unit. If g is 0, there is a Q unit. This nomenclature is known to those skilled in the art, for example from W. Noll's Chemie und Technologie der Silicone, Verlag Chemie, Weinheim Bergstr., 1960, page 2 and one or more subsequent pages thereof.

[0079] An alternative representation of the building block according to formula (A) is:

[0080]

[0081] This alternative representation of the building block according to formula (A) highlights the bridging function of the oxygen atoms bonded to the silicon atoms, which oxygen atoms are usually shown as "O" in other depictions of the building block according to formula (A). (3-m / 2) ” and “O (3-n / 2)The free valencies of these oxygen atoms (indicated by the bond to the wavy line) can be satisfied by any suitable partner, preferably by silicon atoms of other building blocks according to formula (A) and / or (B). If the free valencies are satisfied by silicon atoms of other building blocks according to formula (A) and / or (B), the bis-silyl compound is an oligomer or polymer.

[0082] Similarly, an alternative representation of the building block according to formula (B) can be depicted as follows:

[0083]

[0084] An exemplary oligomer of a bis-silyl compound consisting of three building blocks according to formula (A) is described below. In this depiction, three building blocks are highlighted by a rectangular box with dashed lines to further illustrate the concept of building blocks. The building blocks are connected by bridging oxygen atoms.

[0085]

[0086] As described above, the 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 above silanes, the alkoxy groups are cleaved, which facilitates the formation of the siloxane bonds ("Si-O-Si") described above. These siloxane bonds include a bridging oxygen atom located between two silicon atoms of each building block.

[0087] Preferably, the amount of at least one bis-silyl compound in the composition 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 amount of the composition. If more than one bis-silyl compound is included in the composition, the amount of all bis-silyl compounds is preferably within the above defined range.

[0088] The composition according to the invention comprises at least one slip agent. The at least one slip agent is selected from waxes, fatty acids and fatty acid esters. Preferably, the at least one slip agent is a wax, more preferably, the at least one slip agent is selected from amide waxes, polyolefin waxes and copolymers thereof, even more preferably from polyolefin waxes and copolymers thereof, yet even more preferably polyolefin waxes, yet even more preferably polyethylene waxes. The preferences outlined are such that the composition according to the invention has an increased scratch resistance and improved stability. In addition, when fatty acids and fatty acid esters are used as at least one slip agent, they do not give the same lasting effect as waxes.

[0089] The wax is preferably selected from natural waxes and synthetic waxes. Natural waxes include recent waxes such as beeswax, carnauba wax or candelilla wax, fossil waxes such as montan wax or its derivatives, and petroleum waxes (paraffin wax and microcrystalline wax).

[0090] The synthetic wax is preferably selected from Fischer-Tropsch waxes, polyolefin waxes (e.g. polyethylene waxes, polypropylene waxes, polyisobutylene waxes and copolymers thereof), amide waxes (e.g. N,N'-distearic acid ethylenediamine), polyethylene glycol waxes and polypropylene glycol waxes. 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.

[0091] For better dispersibility, nonpolar waxes such as petroleum waxes, Fischer-Tropsch waxes and polyolefin waxes such as polyethylene waxes are preferably used in their oxidized form. Such oxidized waxes have been known for a long time and can be prepared by standard methods.

[0092] For the purposes of the present invention, polyethylene wax (sometimes also referred to in the art as "polyethylene") is particularly preferred. The number average molecular weight (M) of the polyethylene wax used is n ) is usually in the range of 400 to 20,000 g / mol (measured by GPC, PLgel column (Agilent), solvent: 1,2,4-trichlorobenzene + 0.015 wt% of butylated hydroxytoluene, 160° C., using polyethylene standards provided by Agilent). Preferably, M n 500-15,000 g / mol, more preferably 1000-8000 g / mol. Said range leads to improved stability and enhanced scratch resistance of the composition according to the invention.

[0093] Preferably the polyethylene wax has a melting point of 50-170° C., preferably 80-150° C., more preferably 100-135° C. The melting point is measured according to DIN 51532 (2012). Said range leads to improved stability and enhanced scratch resistance of the composition according to the invention.

[0094] The polyethylene optionally has a certain degree of branching, which in the case of short-chain branching may also result from the use of olefinic comonomers such as propylene, 1-butene or 1-hexene.

[0095] There are many methods known to those skilled in the art how to prepare polyethylene waxes. Polyethylene waxes of various types thereof are commercially available, also in the form of aqueous dispersions. Illustratively, they can be prepared by thermal degradation and, if appropriate, free radical degradation of higher molecular weight polyethylene, or by polymerization of ethylene by means of a free radical mechanism or a transition metal catalyst.

[0096] In order to improve the dispersibility of polyethylene wax and therefore improve the stability of the composition according to the present invention, it is advantageous to use a copolymer comprising 50 mol % or more of ethylene and 50 mol % or less of polar monomers, such as ethylene-vinyl acetate copolymer wax or ethylene and acrylic acid copolymers. Another possible method for preparing dispersible polyethylene is to graft polyethylene in the melt with unsaturated polar monomers such as maleic anhydride. For this purpose, it is generally useful to add a free radical initiator. If desired, the polyethylene modified in this way can be advantageously easily converted into nonionic, anionic or cationic dispersions by conventional methods after further modification, which is usually achieved by adding one or more emulsifiers (also referred to as "surfactants" in the art, see below).

[0097] The polyethylene wax is preferably selected from the group consisting of a copolymer of a non-modified polyethylene wax, polyethylene and polyethylene grafted with at least one polar monomer. More preferably, it is selected from a copolymer of polyethylene and polyethylene grafted with at least one polar monomer. These preferred polyethylene waxes are preferably used in their oxidized form as described above.

[0098] There are many commercially available (partial) fatty acid esters which can be used as at least one slip agent, preferably so-called ester waxes. Preferred examples include stearic acid esters or tristearin of ethylene glycol, diethylene glycol, polyethylene glycol or 1,4-butylene glycol, and mixed partial esters of mannitol with stearic acid and palmitic acid.

[0099] Suitable fatty acids as at least one slip agent have the structure R x -COOH, where R x is C10-C22-alkyl or C10-C22-alkenyl. Preferred examples are oleic acid, stearic acid, palmitic acid and lauric acid.

[0100] Mixtures of glidants can be used in the context of the present invention. For example, wax and fatty acid or wax and (partial) fatty acid esters or any other combination can be used as at least one glidant.

[0101] The amount of at least one glidant in the composition is preferably 0.01 or 0.05 to 5 wt %, more preferably 0.1 to 2 wt %, based on the composition. In the case where more than one glidant is used in the composition, the total amount of all glidants is preferably within the above range.

[0102] Preferably, the composition according to the invention comprises, in addition to at least one bis-silyl compound, at least one silane-based compound comprising at least one building block according to formula (I):

[0103]

[0104] in

[0105] Each R y1 are independently selected from hydrogen, alkyl, polyether and aryl groups,

[0106] R y2 is an alkyl group,

[0107] R y3 is an alkanediyl group,

[0108] R y4 is selected from hydrogen, alkyl, aryl and alkaryl,

[0109] Each R y5 are independently alkanediyl,

[0110] R y6 is selected from hydrogen, alkyl, aryl and alkaryl,

[0111] R y7 is selected from hydrogen and alkyl,

[0112] f is selected from 0, 1 and 2

[0113] g is selected from 0 and 1,

[0114] h is selected from 0, 1 and 2,

[0115] The prerequisite is that the sum of f and g is preferably 0-2.

[0116] The silane-based compound further improves the wet scratch resistance.The silane-based compound preferably does not contain any structural units according to formula (A).

[0117] R y1 It is preferably selected from hydrogen and C1-C4-alkyl.

[0118] R y3 Preference is given to C2-C4-alkanediyl.

[0119] R y4 It is preferably selected from hydrogen and C1-C4-alkyl.

[0120] R y7 It is preferably selected from hydrogen and C1-C4-alkyl.

[0121] g is preferably 0. h is preferably 0.

[0122] In a preferred embodiment of the present invention, R y1 is selected from hydrogen and C1-C4-alkyl;

[0123] R y3 is a C2-C4-alkanediyl group;

[0124] R y4 is selected from hydrogen and C1-C4-alkyl;

[0125] R y7 is selected from hydrogen and C1-C4-alkyl;

[0126] g is 0; f is selected from 0, 1, and 2; and h is 0.

[0127] The at least one building block according to formula (I) preferably accounts for at least 50% by weight of the silane-based compound, more preferably 75% by weight, 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 Si-NMR spectroscopy. Other suitable methods are known to the skilled person, such as gel permeation chromatography.

[0128] In the composition according to the present invention, the amount of the silane-based compound is preferably 0.001-20 wt %, more preferably 0.01-8 wt %, even more preferably 0.05-2 wt %, still even more preferably 0.1-1.6 wt %, based on the total amount of the composition.

[0129] The silane-based compounds are known in the art and are commercially available. Useful preparation methods are particularly described in US2018 / 127442A1 (particularly paragraphs 11 to 41 and Examples 1, 2 and 3).

[0130] For the same reasons as outlined for the at least one bis-silyl compound, the at least one silane-based compound is preferably an oligomer or polymer. The details described for the building block patterns described for the at least one bis-silyl compound apply mutatis mutandis to the at least one silane-based compound.

[0131] The weight ratio of at least one silane-based compound to at least one bissilyl compound - if the aforementioned compounds are present in the composition according to the invention - is preferably from 0.1 to 0.9, more preferably from 0.2 to 0.8, even more preferably from 0.3 to 0.7.

[0132] The composition according to the invention preferably comprises water, preferably in an amount of 1 to 99.99 wt.-%, more preferably 10 to 99.9 wt.-%, even more preferably 50 to 99.7 wt.-%, yet even more preferably 90 to 99.6 wt.-%, based on the total amount of the composition.

[0133] The composition according to the invention preferably comprises at least one acid. The at least one acid further improves the stability of the composition. The acid is typically a Bronsted acid having a sufficiently high pK aThe at least one acid is generally selected from inorganic acids and organic acids. Preferred inorganic acids are selected from nitric acid, hydrochloric acid, methanesulfonic acid and mixtures thereof.

[0134] Organic acids are preferred and are preferably selected from monocarboxylic acids and dicarboxylic acids. The acid is preferably unsubstituted. Monocarboxylic acids are more preferred as the at least one acid because they surprisingly improve the wetting of the substrate glass surface, 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 the at least one acid is even more preferably selected from acetic acid and formic acid. Most preferred in this respect is formic acid because it performs well in this respect.

[0135] The amount of the at least one acid may be based in particular on the amine number of the at least one bis-silyl compound (and the amine number of the at least one silane-based compound, if present). Preferably, the amount of the at least one acid is from 0.00001 to 10% by weight, more preferably from 0.01 to 1% by weight, even more preferably from 0.2 to 0.1% by weight, based on the total amount of the composition.

[0136] The pH value of the composition according to the invention is generally between 1 and 14. The pH value of the composition according to the invention may be between 1 and 7, more preferably between 3.5 and 6.8, even more preferably between 4.5 and 6.5. Said pH range advantageously improves the stability of the composition according to the invention. In the case where the substrate to be treated comprises a glass surface, the preferred pH range avoids potential glass corrosion, and it has been found that in some cases, if the pH value of the composition is >7, the scratch resistance may deteriorate.

[0137] The composition optionally comprises 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 and ethanol. If present in the composition of the present invention, one or more optional organic solvents are preferably included in a total amount of 25 wt % or less based on the total amount of the composition, more preferably in an amount of 20 wt % or less, even more preferably in an amount of 15 wt % or less, also even more preferably in an amount of 1.0 wt % or less, also even more preferably in an amount of 0.25 wt % or less. Ideally, the amount thereof is less than 0.1 wt %, because this further improves the ecological impact of the present invention. In particular (for ecological and safety reasons), based on the overall composition according to the present invention, the amount of the alkanol in the composition according to the present invention is preferably 1 wt % or less, preferably 0.25 wt % or less, ideally 0.1 wt % or less.

[0138] The composition is preferably a dispersion. A dispersion in the context of the present invention is preferably an emulsion or a suspension. It is preferably an emulsion which facilitates the treatment of at least one glass surface therewith, in particular if the composition is applied by spraying since clogging of the nozzle of the spray application device is avoided.

[0139] Typically, and in particular where the composition is a dispersion (e.g., an emulsion), the composition according to the invention preferably comprises at least one emulsifier (also referred to 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 of a person skilled in the art and routine experimentation. The at least one emulsifier is preferably included in the composition according to the invention in an amount of 0.01 to 10% by weight, more preferably 0.1-2.5% by weight, even more preferably 0.2-1.0% by weight, based on the overall composition according to the invention. If more than one emulsifier is included, the total amount of all emulsifiers is preferably within the above range. Preferably, the at least one emulsifier has an HLB value of 8 or more, more preferably 11 or more.

[0140] Useful emulsifiers are selected from nonionic, anionic, cationic, amphoteric emulsifiers and mixtures of the aforementioned substances. The at least one emulsifier is preferably selected from nonionic, anionic, cationic emulsifiers and mixtures of the aforementioned substances, more preferably selected from nonionic and cationic emulsifiers and mixtures of the aforementioned substances.

[0141] Preferred examples of nonionic emulsifiers are represented by formula (E):

[0142]

[0143] in

[0144] R E1 is C8-C22-alkyl;

[0145] R E2 is selected from the group consisting of hydrogen, alkyl, hydroxyl and oxyalkyl;

[0146] each E is independently an alkanediyl group; and

[0147] e is an integer from 1 to 100.

[0148] R E1 Preferably, R E1 is a branched alkyl group. Most preferably, R E1 is iso-C13-alkyl. E2 Preferably, R is selected from hydroxy, oxymethyl and methyl. More preferably, R E2is a hydroxyl group. E is preferably selected from 1,2-ethanediyl, 1,2-propanediyl and 1,3-propanediyl. e is preferably 2-10, preferably 3-7, more preferably 4-6.

[0149] Preferably, the anionic emulsifier is represented by formula (L)

[0150] R L -L (L)

[0151] Where R L is C8-C22-alkyl; and

[0152] L is selected from a carboxylic acid group (-CO 2 H), sulfonic acid group (-SO 3 H) and phosphonic acid groups (-PO 3 H 2 ) or a salt thereof.

[0153] R L Preferably, R 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 of the invention as defined above may cause the anionic emulsifier to lose its water solubility and thus may result in a less stable composition.

[0154] The cationic emulsifier is preferably represented by formula (T)

[0155] R T -T (T)

[0156] in

[0157] R T is C8-C22-alkyl; and

[0158] T is a cationic group, preferably -NR k 4 + Group, where R k is hydrogen or alkyl (which is preferred), such as methyl or ethyl. T Preferred are C10-C18-alkyl, more preferred are C12-C16-alkyl.

[0159] Preferably, the composition according to the invention comprises colloidal silicon dioxide in an amount of preferably 0.01 to 1 wt. %, preferably 0.05 to 0.5 wt. %, more preferably 0.1 to 0.25 wt. %, based on the total weight of the composition (and the solids content of the colloidal silicon dioxide if a dispersion is used). The size of the silicon dioxide particles (d 50) is preferably 10-250 nm, more preferably 20-100 nm. d can be measured by dynamic light scattering according to ISO 22412:2017-02, preferably using Malvern Panalytical 50 Colloidal silicon dioxide can improve the stability of the composition according to the invention.

[0160] Optionally, the composition according to the invention comprises an organic polymer selected from polyurethanes, polyesters, polymethacrylates and mixtures and copolymers of the foregoing. The amount of the organic polymer is preferably 0.01-10 wt %, preferably 0.1-5 wt %, more preferably 0.25-1 wt %. After application of the composition according to the invention, the organic polymer enhances the adhesion of the label, paint or ink applied to the surface.

[0161] The solids content of the composition according to the invention is preferably 0.01-15%, more preferably 0.05-10%, even more preferably 0.1-1%.

[0162] In one embodiment of the invention, the composition according to the invention comprises (or consists of):

[0163] I) at least one bis-silyl compound;

[0164] II) at least one slip agent;

[0165] III) at least one emulsifier;

[0166] IV) preferably, at least one acid; and

[0167] V) Water.

[0168] The named components are preferably contained in the compositions according to the invention in the amounts stated above.

[0169] In another embodiment of the present invention, the composition according to the present invention comprises (or consists of):

[0170] I) at least one bis-silyl compound;

[0171] II) at least one slip agent;

[0172] III) at least one emulsifier;

[0173] IV) preferably, at least one acid;

[0174] V) water, and

[0175] VI) at least one silane-based compound.

[0176] The named components are preferably contained in the compositions according to the invention in the amounts stated above.

[0177] Preferably, the composition according to the present invention does not contain any polyisocyanate in an amount of 0.1 wt % or more. More preferably, the composition according to the present invention does not contain polyisocyanates. Polyisocyanates adversely affect the stability of the composition according to the present invention. Polyisocyanates in the context of the present invention are compounds with at least two isocyanate groups (free or blocked, for example oxime blocked). Such polyisocyanates are particularly described in US6,403,175 (column 8, line 1 - column 9, line 7).

[0178] The composition according to the present invention can be prepared by standard and known methods in the art. Illustratively, the components described above can be mixed in a suitable container using standard means. The present invention also relates to a method for preparing a composition according to the present invention, which comprises mixing in a suitable container at least one bis-silyl compound, at least one slip agent and optionally at least one emulsifier, optionally at least one acid and optionally water (and optionally other optional components mentioned above) to obtain a composition according to the present invention.

[0179] In the process of the present invention, it is also possible to prepare a bis-silyl compound as described in US2011 / 02688911A1 (see in particular paragraphs 17 to 174 and Examples 1 to 41 thereof) and to add any possible other components before, during or after its preparation to obtain a composition. Preferably, the at least one slip agent is dispersed before being added to the at least one bis-silyl compound.

[0180] In another aspect, the present invention relates to a kit-of-parts for preparing a composition according to the invention, said kit comprising part A and part B, wherein part A comprises at least one bis-silyl compound and part B comprises at least one slip agent. By mixing part A and part B of the kit according to the invention, the composition according to the invention can be easily prepared. Mixing part A and part B can be achieved by using standard means (see above). The composition thus obtained can optionally be diluted with water and optionally with at least one solvent. For the reasons stated above, water (alone) is preferred.

[0181] Part A preferably comprises water. Part A optionally comprises at least one solvent, if present. Part A of the kit according to the invention preferably comprises at least one acid.

[0182] Part B preferably comprises water. Part B of the kit according to the invention preferably comprises at least one emulsifier.

[0183] The kit according to the invention preferably comprises:

[0184] part A comprising at least one bis-silyl compound, water and at least one acid; and

[0185] Part B comprises at least one glidant, water and at least one emulsifier.

[0186] More preferably, the kit according to the invention comprises (or consists of):

[0187] a part A comprising at least one bis-silyl compound, at least one silane-based compound, water, and at least one acid; and

[0188] Part B comprises at least one glidant, water and at least one emulsifier.

[0189] As may be expected, the concentrations of the components in parts A and B of the kit according to the invention may deviate from those described for the compositions according to the invention.

[0190] The kit according to the invention has two advantages. The components have a very long shelf life and can be stored for a long time even at elevated temperatures such as 40°C. And the kit allows a simple preparation method of the composition according to the invention, without requiring any special equipment.

[0191] The invention also relates to a method for treating at least one glass surface of a substrate, the method comprising the following method steps:

[0192] a) providing a substrate comprising said at least one glass surface; and

[0193] b) treating the at least one glass surface with a composition according to the invention; to obtain a treated glass surface.

[0194] The method of the invention comprises method steps a) and b). These method steps are performed in the order given. The method of the invention optionally comprises further method steps which are performed before, after and / or between the method steps.

[0195] In method step a) of the method of the present invention, a substrate comprising at least one glass surface is provided. The form or function of the substrate is not particularly limited, as long as it comprises at least one glass surface. Preferably, the substrate is made entirely of glass. In one embodiment of the present invention, the substrate consists of at least one glass surface.

[0196] The substrate comprising at least one glass surface is preferably a hollow container, more preferably selected from the group consisting of bottles, thermoses, ampoules, tubes, jars, vials and flasks.

[0197] Glass in the context of the present invention is not particularly limited. Glass includes soda-lime silicate glass, aluminosilicate glass, borosilicate glass, aluminoborosilicate glass, silica glass, etc., but also includes but is not preferred non-silicate glass.

[0198] Optionally, the method comprises a further method step after method step a) and before method step b):

[0199] ai) cleaning the at least one glass surface.

[0200] A variety of methods are available to the skilled person, in particular for the purpose of removing dirt and grease from at least one glass surface. For example, at least one glass surface can be chemically cleaned. Chemical cleaning comprises in particular treating the surface with an (alkaline) aqueous solution containing a suitable surfactant and / or an oxidizing agent. Alternatively, it can be wiped with a cloth, which optionally contains the aforementioned aqueous solution.

[0201] In method step b) of the method according to the invention, at least one glass surface is treated with a composition according to the invention. The at least one glass surface is treated completely with a composition according to the invention, or only one or more parts thereof.

[0202] The temperature of at least one glass surface in method step b) is preferably 20-200° C., more preferably 60-150° C., even more preferably 100 or 110-130° C. Therefore, the glass surface does not need to be heated to as high a temperature as in the case of commonly used tin compounds. Therefore, the method according to the invention saves energy and is more environmentally friendly.

[0203] Optionally, the temperature of the composition is adjusted to a value of 10-80°C, preferably 20-30°C, before the composition is used to treat at least one glass surface.

[0204] Generally, it is recommended to keep the temperature difference between the composition and the glass surface within a certain range. For example, a temperature difference between the composition and the glass surface of 100° C. or more should be avoided. Otherwise, the glass surface may be subjected to treatments that lead to cracking, etc. The permissible temperature difference depends, among other things, on the type of glass used. A person skilled in the art knows this and is able to select a suitable temperature based on his general knowledge or based on routine experiments.

[0205] The at least one glass surface is treated with the composition by conventional methods. Preferably, the treatment of the at least one glass surface in method step b) is carried out by spraying, dipping, rolling, painting and combinations thereof. Spraying is particularly preferred.

[0206] Preferably, the method of the present invention does not use any tin compound, for example tin salts such as n-butyltin trichloride and tin tetrachloride. For this reason, the composition preferably does not contain (intentionally added) tin compounds. This means that the content of tin compounds in the composition according to the present invention is preferably 0.1% by weight or less, more preferably 0.01% by weight or less, even more preferably 0.001% by weight. Ideally, the composition of the present invention does not contain tin compounds at all. In particular, the method of the present invention does not use any tin compound to bind at least one slip agent to at least one glass surface. Omitting tin compounds such as tin salts is environmentally and toxicologically advantageous, as already outlined above.

[0207] In yet another aspect, the present invention also relates to a substrate comprising

[0208] i) at least one glass surface; and

[0209] ii) at least one layer obtained by treating at least one glass surface with a composition according to the invention (hereinafter referred to as "layer ii)").

[0210] Layer ii) is obtained by treating at least one glass surface with the composition of the present invention. Layer ii) has proven difficult to characterize. The inventors of the present invention believe that multiple compounds derived from at least one bis-silyl compound are present in layer ii). The substrate optionally includes one or more other layers located below or on top of layer ii), preferably the optional other layers are located on top of layer ii). Layer ii) is preferably arranged directly on at least one glass surface. Layer ii) is present on the entire glass surface, or only on one or more parts thereof. Optionally, the substrate includes one or more adhesive layers on layer ii). Conventionally used adhesives can be used for this purpose without limitation. The label is optionally located on the optional adhesive layer. The label is typically made of paper or the like. For decorative or informational purposes, it can be printed on the side facing away from the glass surface.

[0211] Preferably, the substrate is a hollow container, more preferably a hollow container selected from the group consisting of bottles, thermoses, ampoules, tubes, cans, vials and flasks.

[0212] In a preferred embodiment of the present invention, the substrate is selected from bottles, thermoses, ampoules, tubes, cans, vials and flasks and comprises at least one glass surface, layer ii) on at least one glass surface, an adhesive layer on layer ii) and a label on the adhesive layer.

[0213] In yet another aspect of the present invention, the substrate according to the present invention, in particular a hollow container as a substrate, is used for storing a fluid or a solid therein, preferably a fluid, more preferably a liquid, even more preferably a beverage, such as water.

[0214] The invention will now be illustrated by reference to the following non-limiting examples. DETAILED DESCRIPTION

[0215] Example

[0216] Unless otherwise stated below, commercial products are used as described in the technical data sheets available on the filing date of this specification. Unless stated differently below, the latest version of the standard applies.

[0217] As glass substrate, untreated 1 liter soda-lime-silicate glass bottles were used in all experiments. As manual applicator, a spray gun (IPOTOOLS Mini HLVP Spray Gun) was used.

[0218] The following products were used as slip agents in the following experiments:

[0219]

[0220] All slip agents are aqueous dispersions of oxidized or partially oxidized polyethylene.

[0221] Test Method

[0222] Dry and wet scratch resistance - scratch test

[0223] The scratch resistance is tested by rubbing the surfaces of two coated glass bottles against each other, one bottle in each hand. The test is repeated several times by at least two individuals on various areas on the glass bottles. The resistance to scratching or sliding is recorded. The wet scratch resistance is tested in the same way as the dry scratch resistance, but the glass surfaces are wetted with water beforehand. For this purpose, the glass surfaces are wetted in rinse water. The pressure and the scratching time (15 s) are kept constant.

[0224] Grading: No scratches: 1, Slight scratches: 2, Scratches on the entire test surface: 3

[0225] Optical appearance

[0226] The optical appearance was visually inspected by at least two individuals. The optical appearance was graded by turbidity using the following scale: clear (1), slightly turbid (2), and turbid (3).

[0227] Determination of the Drying Residue (Solids Content): The solids content (also called drying residue) of the formulations was determined as follows: 1.000 g of a sample was weighed out into a small porcelain dish and dried in a drying cabinet at 105° C. until the weight was constant.

[0228] Determination of amine content

[0229] 150-400 mg of sample (depending on the amine content) was weighed into a 150 ml beaker and dissolved with 90 ml of acid (conc.). The resulting solution (c(HCl O)) was titrated with a solution of perchloric acid in acetic acid. 4 )=0.1Mol / l, and tested with effect diagram. Potassium hydrogen phthalate was used to measure the factor of perchloric acid solution.

[0230] calculate:

[0231]

[0232] V = perchloric acid in mL

[0233] c = concentration of perchloric acid in mol / l

[0234] f = factor of perchloric acid

[0235] E = sample amount in grams

[0236] Determination of free alcohol content in the composition:

[0237] Alcohol determination was performed by gas chromatography (column: RTX200 (60 m), temperature program: 90° C. for 10 min-25° C. / min to 240° C., detector: FID, injection volume: 1.0 μl, internal standard: 2-butanol).

[0238] The pH value was measured according to DIN EN ISO 10523 (2012).

[0239] The viscosity is measured according to DIN 53015 (2019).

[0240] Preparation Example

[0241] Comparative Preparation Example 1

[0242] 80.0 g of water were added to the reactor under a nitrogen atmosphere. 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 formulation containing the silane oligomer thus obtained formed a transparent colorless liquid and had the following analytical and physical data:

[0243] Solid content: 7.4% by weight

[0244] Free ethanol content: 13% by weight

[0245] NH 2 Amine content: 1.5% by weight

[0246] Viscosity: 3.0mPas

[0247] pH: 11.0

[0248] Comparative Preparation Example 2

[0249] Comparative Example 1 was repeated using 80 g of an aqueous solution containing 5.4 g of 85% by weight formic acid instead of water. The formulation containing the silane oligomer thus obtained formed a clear, colorless liquid and had the following analytical and physical data:

[0250] Solid content: 12% by weight

[0251] Free ethanol content: 13% by weight

[0252] NH 2 Amine content: 1.48 wt%

[0253] Viscosity: 2.9mPas

[0254] pH: 4.5

[0255] Comparative Preparation Example 3

[0256] Comparative Example 1 was repeated using 20 g of (3-aminopropyl)dimethoxymethylsilane instead of the above silane. The formulation containing the silane oligomer thus obtained formed a transparent colorless liquid and had the following analytical and physical data:

[0257] Solid content: 14.4% by weight

[0258] Free methanol: 7.9 wt%

[0259] NH 2 Amine content: 1.97 wt%

[0260] Viscosity: 3mPas

[0261] pH: 11.2

[0262] Preparation Example 1: Preparation of Bis-Silyl Compound 1

[0263] 300 g of deionized (DI) water and 5.8 g of aqueous formic acid solution (85 wt %) were added to the reactor and heated to 65° C. 45 g of bis[3-(triethoxysilyl)propyl]amine were added to the solution over 30 minutes. The reaction mixture was stirred at 65° C. for 3 hours until the silane was completely hydrolyzed. If necessary, the pH value was adjusted to about 4.3 with formic acid (using the above aqueous formic acid solution). About 60 g of ethanol / water were then removed under reduced pressure (130-200 mbar). If necessary, the resulting solution was diluted with DI water to obtain 300 g of solution. The solution thus obtained containing the bis-silyl compound formed a transparent yellow liquid and had the following analytical and physical data:

[0264] Solid content: 8.9% by weight

[0265] Free ethanol content: 1.6 wt%

[0266] Amine content calculated as NH 2 : 0.48%.

[0267] pH: 4.3

[0268] Preparation Example 2: Preparation of silane-based compound 1

[0269] Charge 340.2 g of DI water in a nitrogen atmosphere into a 4-neck flask equipped with a stirrer, a dropping funnel, and a distillation column with a bridge. Heat the water to 40 °C, and then slowly add 340.0 g of 3-aminopropyltriethoxysilane. The temperature of the reaction mixture rises to about 63 °C. Immediately after the addition of 3-aminopropyltriethoxysilane is completed, reduce the pressure. Under a reduced pressure of 106 to 105 mbar, 371.9 g of ethanol / water (hydrolyzed alcohol + 75%) is distilled off within 4.75 h. After about 134.9 g is distilled off, a total of 78.3 g of DI water is added dropwise during the distillation for dilution within 2.5 h. The reaction mixture is colorless, transparent, and non-viscous during the distillation and near the end. There are no precipitates and deposits on the edge of the flask. After cooling, exhaust the system with nitrogen. The yield is 389.7 g of a transparent and colorless product.

[0270] Solid content: 44.7 wt%

[0271] Free ethanol content: 0.3 wt%

[0272] Mixture 1 (containing at least one bisilyl compound and at least one silane-based compound):

[0273] Add 192.81 g of DI water and 113.64 g of Preparation Example 2 to the reactor. Stir the mixture and slowly add 26.90 g of formic acid aqueous solution (85 wt%). After the formic acid is completely added, add 666.66 g of Preparation Example 1, and stir the resulting mixture for another 10 minutes.

[0274] Stability test

[0275] Add Mixture 1 to a 200 ml glass bottle equipped with a magnetic stir bar and dilute it with deionized water in the amounts given below. Then, add 2.0 g of a lubricant before shaking the bottle until the contents become homogeneous. Store the bottle at 20 °C for 1 week and regularly check its appearance and stability. The results are given in the table below.

[0276] Table 1: Results of the stability test.

[0277]

[0278] The composition is sufficiently stable to be used for glass processing purposes. The composition of RP40 is turbid, but still stable enough to be used for treating glass (entries D and H, see Application Examples).

[0279] Glass processing methods

[0280] The glass substrates were treated by spraying with a manual applicator. To this end, the bottles were placed on a rotating tray and rotated twice, while the entire surface of the bottles was treated. Prior to the treatment, the bottles were heated in an oven to the temperatures given below. The spraying conditions were:

[0281] Nozzle diameter: 0.8mm

[0282] Applied pressure: 4.5 bar

[0283] Spraying distance: 20-30cm

[0284] Spraying volume: 20ml / min

[0285] Spin duration of about 6-7 seconds

[0286] Bottle temperature 120-124℃

[0287] Application Examples 1-4 (according to the present invention)

[0288] 2.5 g of mixture 1 and 195.5 g of deionized water were added to a 200 ml glass bottle equipped with a magnetic stirring bar. After adding 2.0 g of a slip agent, the bottle was shaken until homogeneous. The pH value of the composition thus obtained ranged from 6.0 to 6.5. After storage at room temperature for 0.5 hours and 24 hours, respectively, as described above, the glass bottles were treated with the composition thus obtained. The results are given in the table below.

[0289] Table 2: Test results of application examples 1-4.

[0290]

[0291] Application Examples 5-8 (according to the present invention)

[0292] 5.0 g of mixture 1 and 193.0 g of deionized water were added to a 200 ml glass bottle equipped with a magnetic stirring bar. Then 2.0 g of a slip agent was added, and then the bottle was shaken until uniform. The pH value of the resulting composition was 6.0 to 6.5. Then, after storing at room temperature for 0.5 hours, the glass bottle was treated with the obtained composition. The results are given in the table below.

[0293] Table 3: Test results of application examples 5-8.

[0294]

[0295] Comparative Application Example 1 (One-step method)

[0296] By providing 98 wt% water and adding aminopropyltriethoxysilane (AMEO) at the concentration given in the table below and 1 wt% SC 100 while stirring to prepare an application mixture. The application mixture thus obtained was used to treat glass bottles. The results are given in the table below.

[0297] Table 4: Test results of comparative application example 1.

[0298]

[0299] Both the dry and wet scratch resistances are inferior to those obtained when using the compositions according to the invention.

[0300] Comparative Application Example 2 (Two-step method)

[0301] A solution of each of Comparative Preparative Examples 1 to 3 was prepared by diluting it with water to the concentration given in the table below (column entitled "Amount of silane oligomer in spray solution [wt %]"). A dilution of the slip agent (1 g of silane oligomer diluted with 99 g of water) was used. SC 100). First, the bottles were treated with the spray solution of the comparative preparation example and then with the dilution of the slip agent. The results are given in the table below.

[0302] Table 5: Comparative Examples.

[0303]

[0304] CPE = Comparative Preparation Example

[0305] The results of the application examples clearly show that the compositions according to the invention improve the scratch resistance of glass surfaces treated therewith compared to glass bottles treated by prior art methods. In particular, the wet scratch resistance is significantly enhanced. Surprisingly, some compositions also show enhanced results when stored for a longer period of time (#1 and #2).

[0306] Furthermore, in the case of the inventive examples, the adhesion of the labels was excellent and mostly better than those of the comparative examples (see the results given in Table 2). It is also beneficial that the properties of the bottles are not impaired, such as their optical appearance or their (basic) strength.

[0307] Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification or practice of the invention disclosed herein.It is intended that the specification and embodiments be considered exemplary only, with the true scope of the invention being limited only by the following claims.

Claims

1. A composition for treating at least one glass surface, comprising: a) at least one bissilyl compound comprising at least one building block according to formula (A) in Each R a1 are independently selected from hydrogen, alkyl, polyether and aryl groups, Each R a2 are independently alkanediyl, R a3 is selected from hydrogen, alkyl and aryl, m is an integer from 0 to 3, n is an integer from 0 to 3, as well as b) at least one slip agent selected from the group consisting of waxes, fatty acids and fatty acid esters.

2. The composition according to claim 1, It is characterized in that The at least one bissilyl compound is present in the composition in an amount 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 amount of the composition.

3. A composition according to any one of the preceding claims, It is characterized in that The at least one bis-silyl compound is an oligomer or a polymer.

4. A composition according to any one of the preceding claims, It is characterized in that The at least one slip agent is a wax, preferably the at least one slip agent is selected from amide waxes, polyolefin waxes and copolymers thereof, more preferably selected from polyolefin waxes and copolymers thereof, even more preferably polyolefin waxes.

5. The composition according to claim 4, It is characterized in that The at least one slip agent is polyethylene wax.

6. A composition according to any one of the preceding claims, It is characterized in that The at least one slip agent is present in an amount of 0.01 to 5% by weight, preferably 0.1 to 2% by weight, based on the composition.

7. A composition according to any one of the preceding claims, It is characterized in that R a1 is selected from hydrogen and C1-C4-alkyl, R a2 is a C2-C4-alkanediyl group, and R a3 is selected from hydrogen and C1-C4-alkyl.

8. A composition according to any one of the preceding claims, It is characterized in that The composition comprises water.

9. A composition according to any one of the preceding claims, It is characterized in that The composition comprises at least one silane compound based on at least one structural unit according to formula (I) in Each R y1 are independently selected from hydrogen, alkyl, polyether and aryl groups, R y2 is an alkyl group, R y3 is an alkanediyl group, R y4 is selected from hydrogen, alkyl, aryl and alkaryl, Each R y5 are independently alkanediyl, R y6 is selected from hydrogen, alkyl, aryl and alkaryl, R y7 is selected from hydrogen and alkyl, f is selected from 0 and 1, g is selected from 0, 1 and 2, h is selected from 0, 1 and 2, The prerequisite is that the sum of f and g is preferably 0-2.

10. A composition according to any one of the preceding claims, It is characterized in that The pH value of the composition according to the present invention is 1-7, preferably 3.5-6.8, more preferably 4.5-6.

5.

11. A composition according to any one of the preceding claims, It is characterized in that The composition comprises or consists of the following substances: I) at least one bis-silyl compound; II) at least one slip agent; III) at least one emulsifier; IV) the at least one acid optionally present, and V) Water.

12. A composition according to any one of the preceding claims, It is characterized in that R a3 For hydrogen.

13. A kit for preparing a composition according to any one of the preceding claims, said kit comprising part A and part B, wherein part A comprises the at least one bis-silyl compound and part B comprises the at least one slip agent.

14. A method for preparing a composition according to any one of claims 1 to 12, said method comprising mixing in a suitable container said at least one bis-silyl compound, said at least one slip agent and optionally said at least one emulsifier, optionally said at least one acid and optionally water to obtain a composition according to any one of the preceding claims.

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

16. A substrate, include: 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.

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