SK75694A3 - Hardening method of fragile oxide substrate, composition on silane base and fragile oxide substrate with polymerizating cross-linked siloxane cover - Google Patents

Abstract

A method is described for strengthening or restoring strength to a brittle oxide substrate which includes the steps of coating the brittle oxide substrate with an aqueous solution containing a silane-based composition, and curing the coating to form a transparent layer on the brittle oxide substrate. Also disclosed are novel compositions used to coat brittle oxide substrates, and silane-coated brittle oxide containers.

Description

Technical field

The invention relates to a method for strengthening a brittle oxide material substrate, aqueous solutions containing silane-based compositions, and brittle oxide material substrates coated with a co-polymerized crosslinked siloxane. In particular, the invention relates to a method of strengthening a brittle oxide substrate, such as a glass container, or to restoring the strength of a brittle oxide substrate, such as a glass container, or partially or completely healing the failures on a surface resistant to a certain stress. material such as glass containers coated with a co-polymerized crosslinked siloxane and compositions suitable for coating on these brittle oxide substrates, such as glass substrates.

BACKGROUND OF THE INVENTION

WITH

Fragile materials, such as glass substrates, usually exhibit certain mechanical properties, such as tensile strength, which are significantly less than theoretically predicted values. This may be due to factors such as irregularities in the structure of the test sample or a low content of contaminants, either inside or on the surface of the material from which the test article is made. According to the prior art, in the case of brittle metal materials, in an attempt to improve the mechanical properties of these brittle metals, a progressive band-melting (zonal) melting method has been developed in which the crystalline structure of this material has been reformed and pollutants are washed out of the fused brittle material. In addition, a prior art method has been developed to improve the mechanical properties of non-metallic brittle materials by applying a multilayer structure to the brittle non-metallic material. In order to protect various brittle materials from scratches or other abrasions, a method of surface treatment of these brittle materials has been further developed, by means of which it is possible to achieve to some extent the consolidation of this brittle material.

In fact, glass is one of the strongest materials known to mankind. In theory, standard silicate glass should withstand a voltage of up to about 14 GPa to up to about 20 GPa. In a practical situation, however, this strength is much less, around 70 MPa.

The explanation for this significant discrepancy between the theoretically determined strength value and the actual measured value lies in the existence of surface defects, cracks or scratches. These defects substantially disrupt the siloxane structure (Si-O-Si bonds) that form the backbone of the glass material. This damage to the glass will cause all the applied stress to be concentrated there and cause destructive damage to the glass product, which usually occurs at much less stress than the expected stress at which the material should break. Although the above considerations have been made in connection with glass products, the same theoretical justification can be applied to any brittle material that does not exhibit substantial plastic deformation prior to damage.

In the case of glass containers, for example, surface defects or defects may come from many different sources, whether they are molten residues of the starting materials remaining in the final product or scratches caused by contact with hard surfaces, including other glass products. the glass products of their manufacture, and the moisture guide rails, can hardly be damaged by handling from the very beginning Contact with particles of various solid materials from the air, hitting other glass products, on-other handling equipment and constant contacts with the conveyor belt, glass products.

that can be led. to the considerable containers relative to the formed ones, they convey these drop defects in the glass strength of these surfaces

According to the long performed glass. Up to now the prior art are already alleviating these strength problems, the preparation of these glass by these products has led to researches as. but all unsatisfactory glass products remained for research efforts to reduce these defects must necessarily occur on the surface of said materials.

solutions regarding the handling and result of the products, because the surface handling of products increase the strength of these solutions still defects. For this reason, the effect of these defects was if

A certain effort to improve the strength of glass products is to provide a solution according to U.S. Pat. No. 4,859,636 to Aratani et al., Which is based on the replacement of metal ions in the glass by ions of greater radius, thereby inducing surface compressive forces. U.S. Pat. No. 3,743,491 to Poole et al. Also refers to surface compression forces, but this patent proposes the application of a polymeric protective coating to protect the surface from further abrasion. U.S. Pat. No. 4,891,241 to Hashimoto et al. Relates to the treatment of a glass surface with a silane coupling agent followed by the application of a polymer coating containing acryloyl and / or methacryloyl groups, followed by irradiation or heat treatment of the surface to co-polymerize the molecules containing these groups . In this U.S. Pat. No. 4,891,241 it is also stated that this silane coating alone is not sufficient to consolidate said substrates, and it is necessary to use acrylates to consolidate these surfaces.

Although some improvements in the strength of glass substrates are achieved when applying the solution of the patents, these methods are not without drawbacks. In some of these methods of processing glass substrates, longer time intervals than those available in the manufacture of these glass products are necessary, which means that it is necessary to use processing lines outside the actual glass product manufacturing process. The safety and health of workers in these operations should also be taken into account when applying these methods. In particular, the need to care for the safety and health of workers in these products results from the use and handling of organic solvents as well as acrylate and methacrylate compounds.

It follows from the above that there is an urgent need in the art to develop a method of consolidating brittle substrates of oxide materials that solves the problems encountered in applying prior art methods and by which an acceptable increase in strength of such brittle oxide substrates can also be achieved. There is also a need in the art for a brittle coated substrate of oxide coated material to achieve a strength improvement that is substantially higher than that of a brittle oxide substrate without any coating.

Further, there is a need in the art to develop a method of consolidating a brittle substrate of an oxide material by which a substrate with acceptable marking and / or moisture resistance can be produced.

Further, there is a need in the art to develop a substrate of brittle oxide material with a co-polymerized crosslinked siloxane coating in which the cured coating is transparent.

Other objects and advantages of the present invention will be in part apparent from the following description, or may be inferred therefrom, or ascertained from the practice of the invention. These objects and advantages of the present invention can be achieved by means of features and combinations of features particularly resulting from the following claims.

SUMMARY OF THE INVENTION

In order to achieve these objects and needs arising from the drawbacks of the prior art, the present invention has been developed, which will be described in detail below, and which relates to a method of consolidating a brittle substrate of an oxide material comprising the following steps. First, the brittle oxide substrate is coated with an aqueous solution containing a silane-based composition. The aqueous solution containing the silane-based composition is substantially free of any organic solvent. Further, this silane-based composition has the following general formula when hydrolyzed in this aqueous solution:

(oh) ₃ sulfur ² wherein R ^{2 is an} organofunctional group.

After the coating of the aqueous solution containing the hydrolyzed silane-based composition is applied to the brittle oxide substrate, the coating cures to form a transparent layer on the brittle oxide substrate. It is to be noted that the substituents R ² are selected such that:

(i) substantially improved the strength of said brittle oxide substrate having said cured coating on its surface compared to the strength of the brittle oxide substrate prior to application of said coating; and (ii) that said cured coating does not adversely affect the marking ( the adhesive ability of this brittle oxide substrate.

The invention also relates to an alternative process, which is similar to the above procedure except that R ² is chosen such that:

(i) substantially improve the strength of said brittle oxide substrate having said cured coating on its surface compared to the strength of the brittle oxide substrate prior to application of said coating; and (ii) thereby obtaining a substantially reinforced oxide substrate thus obtained. The cured coating material on its surface maintained a moisture resistance of at least about 50%.

The present invention relates to a material coated with a siloxane coating, the oxide vessel also relates to the layer vessel

Specifically, the brittle oxide siloxane material of the brittle layer applied to a co-polymerized co-directional crosslinked vessel is that the brittle layer co-polymerized on the surface of the oxide substrate vessel and the crosslinked siloxane crosslinked consists of transparent which is preferably on the outer surface of the vessel of brittle oxide material cured. The co-polymerized crosslinked siloxane according to the invention is formed from a silane-based composition hydrolysed in an aqueous solution which is substantially free of organic solvent. For example, the silane-based composition may be selected from the group consisting of methacryloxypropyltrimethoxysilane (MPTMO), glycidoxypropyltrimethoxysilane (GPTMO), vinyltrimethoxysilane (VTMO), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (CETMO), CETMO), dimethoxypropyltrimethoxysilane (DPTMO), 5,6-epoxyhexyltrimethoxysilane (EHTMO), N- (trimethoxysilylpropyl) maleic acid amide, 3-ureidopropyltrimethoxysilane (UPTMO), 1,2-bis (trimethoxysilyl) ethane, BTMM -trimethoxysilylpropoxy) ethane (BTMOPE), hydrolyzed forms of these compounds, and mixtures of these compounds.

The invention also relates to novel silane compositions, including, but not limited to, a mixture of vinyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, a mixture of methyltrimethoxysilane and 2- (3,4-epoxycyclohexyl). -ethyltrimethoxysilane, a mixture of glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and methyltrimethoxysilane, and a mixture of glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

By means of the above-described invention, it is possible to overcome the problems encountered in handling and handling brittle substrates of an oxide material such as glass. By the method of the present invention, the strength of brittle substrates made of an oxide material can be greatly increased and quite unexpectedly recovered compared to the strength of the brittle substrate it had before coating. In addition, it is noted that the coatings of the present invention are transparent and safe when applied to brittle oxide substrates. It is further important that by increasing or restoring the strength of the substrate by the above coating, the coating does not have a preferred embodiment. adversely affecting the marking ability, which was a problem of coatings applied to similar substrates according to the prior art.

It is to be understood, of course, that the foregoing description and the following detailed embodiment of the present invention are merely exemplary and illustrative of certain features of the present invention and are not intended to limit the scope of the present invention.

The brittle oxidic substrate used in the process of the present invention may be prepared from any brittle oxidic material such as aluminum oxides or aluminates, silicon oxides or silicates, titanium oxides or titanates, germanates, or the glass may be made for example from the aforementioned materials. In addition, it should be noted that the brittle oxide substrate may be in any form, for example a glass bottle.

The silane-based composition has the following general formula when hydrolysed in aqueous solution:

(OH) ₃ SiR ² wherein R ² is an organofunctional group that is. it may or may not be hydrolyzed in aqueous solution. The organofunctional group may be hydrolyzable silane residues. The choice of this organofunctional group R ² further depends on such a requirement that the resulting aqueous solution containing the composition based on hydrolyzed silane, after being applied to the surface of the brittle oxide substrate and cured, can achieve a substantial improvement in the strength of the and wherein the group, when incorporated into the composition and cured after application of the solution to the substrate, does not adversely affect the marking (or labeling) of the brittle oxide substrate.

Preferably R ² includes glycidoxypropyl, 2- (3,4-epoxycyclohexyl) ethyl, 3,3-dimethoxypropyl, 3-ureidopropyl, and hydrolyzed forms thereof.

Accordingly, preferred hydrolyzed silane compositions include hydrolyzed glycidoxypropyltrimethoxysilane, hydrolyzed 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, hydrolyzed 3-ureidopropyltrimethoxysilane, and hydrolyzed silane compositions.

3,3-dimethoxypropyltrimethoxysilane.

The coating applied to the brittle oxide material substrate may also be a mixture of one or more of the above-described silane-based hydrolyzed compositions. Particularly preferred is the use of a mixture comprising two or more hydrolyzed silane-based compositions, provided that one of these hydrolyzed silane-based compositions is known to provide excellent marking capability of the resulting substrate and the other hydrolyzed silane-based composition provides excellent ability to improve the strength of the substrate. In this way, it is possible to achieve the desired balance of the properties with the aid of a given mixture, i.e., the coating provides both improved strength and does not adversely affect the marking ability of the material. In this regard, for example, a suitable mixture of hydrolyzed CETMO, e.g. no. 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and MTMO, m.p. no. methyltrimethoxysilane to achieve an appropriate balance of the above properties.

based on silane or more, hydrolyzed can be used in the form of mixtures with one silane-based composition, methacryloxypropyltrimethoxysilane,

As a further example of hydrolyzed compositions which can be hydrolyzed hydrolyzed

3-ureidopropyltrimethoxysilane, hydrolyzed 1,2-bis (trimethoxysilyl) ethane, hydrolysed 1,2-bis (3-trimethoxysilylpropoxy) ethane, hydrolyzed 5,6-epoxyhexyltrimethoxysilane, hydrolyzed N- (trimethoxysilylpropyl) maleic acid, hydrolyzed amethylenethanedioetisethanethoxysilate, hydrolyzed N - (3-triethoxysilyl propyl) -4-hydroxybutyramide (HBTEO). For example, these compositions can be used in admixture with hydrolyzed CETMO, i. no. 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and / or with hydrolyzed GPTMO, i. no. glycidoxypropyltrimethoxysilane, and / or with hydrolyzed DPTMO, i. no. 3,3-dimethoxypropyltrimethoxysilane. Usually, the silane-based compositions used in the form of a mixture are added in equivalent proportions. However, it will be appreciated that if a greater labeling capacity is desired, then a larger proportion of the hydrolyzed CETMO, i.e., a higher proportion, may be used. no. 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane or hydrolyzed GPTMO; no. glycidoxypropyltrimethoxysilane or hydrolyzed DPTMO, i. no. 3,3-dimethoxypropyltrimethoxysilane. In addition, it should be noted that each of the above compositions can be used alone to substantially increase the brittle oxide substrate strength, unless account is taken of the surface marking or labeling capability.

Unless otherwise indicated, said silane-based compositions cited as specific examples of these materials are commercially available from one or more of the following sources: Union Carbide, Dow Corning, Huls America, and PCR Inc.

Although the coatings of the present invention are mixtures of one or more hydrolyzed silane-based compositions, it is also possible to apply the hydrolyzed silane-based compositions separately to the surface of the brittle oxide substrate. For example, a CETMO coating, i. E., May be applied to the surface of a brittle oxidized substrate. no. 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and then a second coating may be applied, whether it is the same (e.g. wherein the first coating of the CETMO-based composition or another MPTMO coating, i.e. methacryloxypropyltrimethoxysilane), the CETMO coating may still be wet or dry, or the application of the second coating may take place after the first coating has cured.

Any number of successively applied coatings can be applied in this manner. In addition, a surfactant may be applied to the surface of the brittle oxide substrate prior to and / or after the coating of the hydrolyzed or multiple silane-based compositions on the surface. this brittle oxide substrate. Any other coating, such as the layer specified in the above-cited U.S. Pat. No. 4,891,241 to Hashimoto.

According to the present invention, it is understood that by applying the coating or coatings of the present invention to the surface of the brittle oxide substrate, it is also meant to apply the coating or coatings of the present invention to any other preformed layer on the brittle oxide material. An example of this pre-formed layer on the surface of the substrate is hot coatings, which are usually carried out in the industrial manufacture of these materials.

The silane-based compositions used in the process of the present invention may be present in an aqueous solution at an average concentration ranging from about 1% to about 99% by weight in water or an aqueous solution, preferably at an average concentration in the aqueous solution. from about 1% to about 30% by weight, and most preferably from about 2% to about 10% by weight.

With respect to the aqueous solution containing the hydrolyzed silane-based composition, it is noted that the amount of water added to the silane-based composition in the preparation of the aqueous solution of the present invention depends on the concentration of the resulting desired aqueous solution. The dilute the desired solution of the hydrolyzed silane-based composition, the more it is necessary to simply apply a larger amount of the aqueous solution containing the hydrolyzed silane-based composition to the brittle oxide substrate in order to improve the strength thereof.

As mentioned hereinbefore, the term solution includes chemical solutions, suspensions, emulsions and mixtures, wherein any or all of the ingredients may be mixed or incomplete.

The aqueous solution containing the hydrolyzed silane-based composition can be prepared immediately at the point of need, which means that the silane-based composition is added to the water in the production facility in which it is applied.

Alternatively, the silane-based composition can be prepared in the form of a pure substance or concentrate, and then diluted at the site of use with water to prepare the desired aqueous solution containing the hydrolyzed silane-based composition ready for use on a brittle oxide substrate.

Further, the aqueous solution containing the silane composition of the present invention is substantially free of organic solvent, meaning that no organic solvent is intentionally added to the solution. However, some organic compounds may be present in this solution as contaminants and / or as by-products of the reaction of the silane-water composition or as a result of the reaction taking place in the aqueous solution during curing. It should further be noted that some commercially available silane compounds may contain organic solvents which, when introduced into an aqueous solution, are diluted such that the percentage of this solvent is approximately equal to or less than the concentration of the silane in the aqueous solution. One example of such substances is UPTMO, i. no. 3-ureidopropyltrimethoxysilane.

Of course, it is known that the addition of a solvent may increase the stability of the solution.

The following reaction scheme outlines two reactions which are believed to take place in the preparation and application of the aqueous solution containing the hydrolyzed silane composition of the present invention:

(R ¹ O) ₃ S1R + 3 H ₂ 0 <----> (OH) ₃ SiR ² 3-R ^ H ---->

----> Si - 0 - Si

In the above reaction, the trialkoxysilane is reacted in water to form trisilanol in solution. The trisilanol in solution may contain oligomers. In the next phase, this trisilanol condenses in solution, resulting in a co-polymerized crosslinked siloxane (Si-O-Si) coating upon curing. This siloxane (Si-O-Si) coating usually contains an organic substituent or substituents, such as a group or groups R ² .

In this reaction scheme, the R 10 group may be any group that can hydrolyze. Examples of these groups that best meet these criteria are:

ABOUT

II

-CH ₃ , -C ₂ H ₅ and -cch ₃

However, other groups which also meet the above criteria and which are well known to those skilled in the art may also be used.

The R group is an organofunctional group which hydrolyzes during the reaction to form the R ² group. The organofunctional group may be the remainder of the hydrolyzable silane. After the hydrolysis reaction, and if the R group is hydrolyzable, the R ² group comprises at least one hydroxyl group OH. If this R group is not hydrolyzable, then the R and R ² groups are the same, which occurs, for example, when the R group is vinyl or methyl. In general, the R group in the above reaction scheme is selected such that the silane-based composition of the present invention provides a suitable balance between improved or restored substrate strength and surface marking or labeling capability. In view of the above, preferred examples of these R groups include glycidoxypropyl, 2- (3,4-epoxycyclohexyl) ethyl and 3,3-dimethoxypropyl. Preferred examples of the R ² groups include hydrolyzed versions of these preferred R groups.

The above reaction scheme is not intended to limit the manner in which aqueous solutions containing silane-based compositions are prepared. Instead of the starting trialkoxysilanes, any hydrolyzable silane can be simply used. For example, halogenosilanes such as substituted trichlorosilanes may be mentioned in this regard.

As mentioned above, after hydrolysis, the R group is changed to an R ² group containing a hydroxyl group OH. For example, in the case of CETMO, i. no. 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and GPTMO, m.p. no. glycidoxypropyltrimethoxysilane, both of which contain an epoxy ring in the R group, upon hydrolysis in aqueous solution, the epoxy ring of the dihydroxy group is opened, the remainder of this R ^{2 being} hydrophobic. It follows from the foregoing that the bag formation group remains with this R ² group, then a balance of hydrophilic properties (provided by OH groups) and hydrophobic properties is achieved. These hydrophilic properties in the R ² group particularly improve the strength and labelability.

The surfactant may be added to the aqueous solution containing the hydrolyzed silane-based composition to improve coverage of the fragile oxide substrate surface with the aqueous solution containing the hydrolyzed silane-based composition, which results in greater consolidation of the brittle oxide substrate and a better appearance thereof. to mention that the addition of only a small amount of surfactant is used to achieve a better spread of the silane-based composition on the surface of the brittle oxide substrate. Particularly suitable in this regard are nonionic surfactants. One possible example of such surfactants is the commercially available Triton X-102 (available from Union Carbide) which is octylphenoxypolyethoxyethanol. Generally, the addition of this surfactant is in the range of about 0.001% to about 1.0% by weight (based on the total weight of the solution). Preferably, an addition of from about 0.01% to about 0.05% by weight (based on the total weight of the solution) of the surfactant is used.

It will be understood by those skilled in the art that other compounds may be added to the aqueous solution containing the silane-based composition to improve wettability in the practice of the present invention. or to achieve other targets, such as UV stability or control of rheological properties.

The pH of these aqueous solutions containing silane-based compositions is usually adjusted to be in the range of about 1.5 to about 12, and preferably the pH is adjusted to a value in the range of about 2 to about 4, since the most stability at these pH values was achieved when testing these aqueous solutions. Typically, the pH of the aqueous solutions containing the hydrolyzed silane compositions is adjusted depending on the R ² group used. The pH of these aqueous solutions can be adjusted to the desired value by addition of a basic or acidic compound.

The aqueous solution thus obtained containing the hydrolyzed silane-based composition may then be aged, whereby the aging may eventually reduce the level of improvement achieved in strengthening the brittle oxide substrate. Surprisingly, it has been found that by brief aging of the hydrolyzed silane-based composition an improvement in their properties can be achieved under certain conditions, as is the case, for example, with GPTMO, e.g. no. glycidoxypropyltrimethoxysilane. However, further aging may deteriorate these properties. The shelf life of these aqueous solutions containing the hydrolyzed silane-based compositions depends on the composition that, in the case of the hydrolyzed composition, the composition. For example, the silane-based aqueous solution is wherein said hydrolyzed silane-based composition is CETMO, i. no. 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, a shelf life of at least 100 days can be utilized without affecting the ability of the composition to substantially improve the strength of the brittle oxide substrate.

The aqueous solutions containing the hydrolyzed silane-based compositions may be deposited or deposited on the substrate surface in any manner such as spraying, dripping, dipping, coating or any other suitable method suitable for applying liquid, vapor or aerosol to the substrate surface. . Preferably, the aqueous solution containing the silane-based composition is applied in the form of a spray in a post-spray stage or as part of a conventional manufacturing and processing process to produce glass containers, such as glass bottles, as described below, using a conventional spray application device.

The coating of the present invention may be applied directly to any surface of the brittle oxide substrate (i.e., the inner surface, the outer surface, or portions thereof) or may be applied to an outer layer that is different from the brittle oxide substrate material. For example, the coating of the present invention can be applied to a layer of tin oxide, titanium oxide, silicon oxide, or other metal oxide, or a mixture of these materials, while the silane-based composition will still be effective in strengthening the brittle oxide substrate .

In the usual manufacture of glass containers, such as glass flasks, these flasks are moved on a conveyor production line, with gradual steps:

(1) a hot coating under the housing, in which a layer of an inorganic tin compound such as tin oxide is applied, (2) a tunnel cooling furnace, (3) a lubricant spray application phase.

Using the process of the present invention, the application of the aqueous solution containing the silane-based composition in a preferred embodiment of the invention is carried out after the glass bottles have left the tunnel cooling furnace, which coating can be considered as a cold coating.

The aqueous solution containing the silane-based composition can be applied to the substrate at any temperature below the boiling point of the aqueous solution, but typically the aqueous solution is applied at room temperature.

In addition, the aqueous solution containing the silane-based composition can be applied to any brittle substrate of an oxidic material (such as a flase) at any surface temperature of the material that is above the freezing point of the aqueous solution, but preferably In an embodiment of the invention, the surface temperature of the brittle oxide substrate is in the range of about 20 ° C to about 200 ° C, and most preferably, the surface temperature of the brittle oxide substrate to which the aqueous solution is applied, in the range of about 50 ° C to about 60 ° C.

After application of the aqueous solution containing the hydrolyzed silane composition to the surface of said brittle oxide material substrate (such as glass bottles), the coated brittle oxide substrate is introduced into a curing unit, such as a curing oven, where to the surface This brittle oxide substrate typically has a temperature of at least about 230 ° C. However, it will be appreciated that certain coatings of silane-based compositions such as BTMOE, e.g. no. With 1,2-bis (trimethoxysilyl) ethane, effective curing can be achieved at surface temperatures below 230 ° C. Once this surface temperature has been reached, the curing process is efficiently started. For example, the surface temperature can be maintained at this minimum temperature of about 230 ° C for about 30 seconds. The curing temperature selected must be sufficiently high to cure the deposited coating on the brittle oxide substrate, but without browning the coating. The determination of this temperature range at which effective curing is carried out depends in part on the R ² group selected. For example, if CETM0 is used, i. 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, for application to a brittle oxide substrate, then at a temperature below about 200 ° C, only a minimal result is obtained, and at temperatures above about 350 ° C, the coating applied becomes charred.

The curing step may be conducted according to the present invention from any source that provides sufficient energy yield when performing the energy application to remove, for example, water or other non-coating reactants on the surface of the treated brittle oxide substrate, provided that: that application of this energy has no adverse effects on either the brittle oxide substrate or the coating material. This curing process, which combines the effect of the applied energy and the time during which the energy is applied, can be carried out with little energy used over a relatively long period of time, or vice versa, using large energy but limited by the above assumption, over a relatively short period of time. Examples of such power sources include microwave irradiation, infrared radiation, ultraviolet (UV) radiation, or exposure of the coating to ambient or elevated temperature, which can be performed in an electric or gas heating furnace at a pressure higher or lower than atmospheric pressure or combinations of these conditions.

After the curing step has been carried out, a commonly used spray application step can be carried out, as described above, in which a polymeric coating, such as polyethylene, is applied to the brittle oxide substrate to achieve surface slippage. The coating produced by the process of the present invention allows at least as good an adhesion of the lubricant as the adhesion of the lubricant carried out in the hot coating step as mentioned above.

With the coating of the present invention, it is possible to achieve sufficient slippage of the surface of the brittle oxide substrate, thereby avoiding the need for an additional spray application step, which is particularly advantageous in the bottle manufacturing process.

By the strength of the material as mentioned above is meant the maximum load of the sample that can withstand the material from breakage and product breakage. There are many methods for determining the strength at which material destruction occurs, depending on the geometric shape of the product and from the use of this product. These methods include the flexural strength test, the vertical load test, the tear strength test (or tear strength test), the strut strength test determined by the concentric ring, and the impact strength test.

Indeed, the process of the present invention achieves truly significant strengthening of the brittle oxide substrate. As mentioned in the prior art, virtually all brittle substrates of oxidic material, particularly glass, are damaged to some extent by minor defects or by the presence of a small amount of contaminants. Since these brittle oxide substrates could theoretically have much greater strength, the process of the present invention can be characterized as a method of restoring the strength of the brittle oxide substrate since the process of the present invention achieves a degree of strength of the brittle oxide substrate that approximates its theoretical strength.

One way to measure the true strength of a brittle, uncoated, or coated aqueous solution containing a hydrolyzed silane-based composition is by a strut-strength test, which is determined by a concentric ring as described in the Journal of Strain Analysis, Vol. 19, No. 3 (1984) and Journal of Non-Crystalline Solids, 38 & 39, p. 419-424 (1980), which is commonly known to those skilled in the art.

Another method for measuring this strength is a tear strength test (or tear strength) at a pressure application, which method is determined according to ASTM Test C-147 using a ramp pressure tester (obtained from AGR, Intl.), which is equally well known to those skilled in the art.

Another method of determining the strength of said brittle oxide substrate is the impact strength test described in the instruction manual supplied with the AGR Impact Tester. This test is commonly known on an industrial scale using an impact strength tester from AGR, Intl. Butler, PA. This strength test is also one of the methods generally known to those skilled in the art.

As mentioned above, when the aqueous solution containing the hydrolyzed silane composition is applied to a brittle oxide substrate, substantial strengthening of the substrate is achieved. This substantial increase in the strength of said brittle oxide substrate can be demonstrated by improved strength values when performing a center-ring strut strength test, a burst (or tear) stress test, a pressure application, or an impact strength test, wherein: these values are better by at least about 10%. In a preferred embodiment of the invention, an improvement in strength of at least about 20% is achieved.

Those skilled in the art will appreciate that if the strength of the frangible substrate or oxide article such as glass articles is increased, smaller amounts of oxide material may be used to prepare the article having substantially the same strength and general mechanical properties. features. Thus, for example, in the particular case where the glass container is a glass bottle, the glass bottle may be lighter than the previously produced bottle unprocessed by the process of the invention. In addition, by increasing the strength of this material, fewer product defects (such as fewer articles destroyed) are achieved under normal industrial handling.

According to the present invention, it is theoretically believed that a co-polymerized crosslinked siloxane bond occurs not only in the applied coating but also between the coating and the surface of the brittle oxide substrate. This coating, when applied to the surface, appears to work to heal cracks on the surface by forming a network of Si-O-Si bonds throughout the surface where these surface defects occur. The formation of siloxane bonds in the region of these defects causes an increase in the breaking stress of the product.

When using coatings to actually restore or increase the strength of a sample that has been previously damaged in some way, it is necessary to minimize the effect of concentrating the stress on the material on the stress-resistant surface of the material in which these defects occur. This requires the partial or complete healing of defects occurring on this stress bearing surface. In the case of glass containers which are tested for strength under pressure, this stress-tested surface is predominantly the outer surface of the bottle, because with increasing pressure the walls of the bottle are pushed outwards. In general, during loading, the surface on which the convex curvature is formed is the outer surface of the test article.

However, it is, of course, possible to increase the load required to damage the sample by impact without necessarily restoring the strength of the substrate. In this method, instead of examining the tensile strength on the side walls, the coating is tested on a surface that is subjected to an impact test. On impact, tensile stresses are usually applied to the inner surface of the container. The mechanism in this case resides in the ability of the coating to absorb impact energy, so that this energy is not transmitted to the substrate in the form of bending stress. The measured impact load required for material failure is greater, but the bending strength of the object remains unchanged.

In the conventional industrial manufacture of glass containers, the substrate is usually coated with a metal oxide film immediately after the manufacture of the product, using the gas-phase chemical elimination method and referred to as hot coating (HEC method). Generally, the coating is a tin oxide coating, but titanium oxide or other metal oxide may also be used as well as other ingredients to improve various physical properties, such as electrical conductivity. The coating typically has a thickness in the range of about 5 nm to about 12.5 nm. With the process of the present invention, it is possible to restore or increase the strength of a damaged glass substrate, whether or not the surface of the material is precoated with the hot-gas deposition layer (HEC method).

With respect to the marking ability (or the ability to apply the label) of this brittle oxide material, it should be noted that certain cured coatings formed from the hydrolyzed silane composition of the present invention do not adversely affect this marking ability, as discussed above. text. This marking ability is measured by the following test for peeling off the label (s) adhered to this surface.

Four corner corners with an area of about 38.7 cm ² were used to perform this test. These labels were weighed prior to their application, after which casein glue was applied

National

Starch).

About 0.6 grams of this type (4242 from the side of the label) was then applied to the bottom of the label with casein type adhesives, which were spread over the surface of the label by rotating a 5 millimeter glass rod or similar shaped device to achieve even distribution * The sticker was then applied by pressure to the surface of the brittle oxide substrate and allowed to dry for at least two hours at room temperature, after which the sticker was peeled off manually at each corner as long as part of the sticker was still peeling off. The coating formed by the process of the present invention was considered acceptable in terms of marking or labeling ability if more than about 50% by weight of the label remained on the surface of said brittle oxide material.

Preferably, the marking performance (expressed as% of the weight of the label that remains adhered to the brittle oxide substrate surface) of the brittle oxide substrate is greater than about 60%, most preferably greater than about 70% by weight.

With this substantial increase in strength achieved by the cured coating on a brittle oxide substrate, the resistance to the harmful effects of moisture should also be maintained. In fact, the moisture resistance test is a convenient way to determine to what extent and how well a coating of the present invention allows a coated brittle oxide substrate to retain its increased or renewed strength. Excellent moisture resistance exhibited by coatings formed from the silane-based compositions of the present invention generally depend on the selected R ² group in the composition. One way to determine the effect of moisture on the coating of the present invention is to compare the strength of the coated brittle oxide substrate, wherein the cured coating on the substrate is less than 3 hours old, at 40% relative humidity, with the strength of the equally coated brittle oxide substrate humidity for 30 days. In the test, the moisture resistance of the cured coatings of the present invention applied to the brittle oxide substrate is only about 50% of the change in strength of the brittle oxide substrate, preferably only about 20%. up to about 30% strength change, most preferably 0 to about 10% strength change of this brittle oxide substrate, which is an excellent result, especially considering the intended use of glass bottles in a high exposure environment humidity, as in the northern regions of the United States.

An interesting fact of the invention is that not all coatings formed from hydrolyzed silane-based compositions exhibited excellent moisture resistance after application to the brittle oxide substrate. For example, when applied to the brittle oxide substrate surface, material hydrolyzed silane-based composition, wherein R ² is vinyl or methyl, and the layer is cured, then the strength of the substrate significantly improve (i.e., reaches the 110% improvement in strength, determined test the buckling strength of using concentric ring , in the case where R ² is vinyl and 200% improvement in strength in the case where R ² represents a methyl group, provided test the buckling strength of using concentric ring) to also achieve excellent improvement of resistance to moisture (i.e. 0 % st strength or 100% strength if R ² is a vinyl group and 0% loss of strength, that is to say 100% strength if R is methyl), but if apply a layer of a hydrolyzed silane-based composition to the surface of the brittle oxide substrate, wherein R ² represents a 2- (3,4-epoxycyclohexyl) ethyl or glycidoxypropyl group, and this layer is cured before the strength of the coated substrate is substantially increased (i.e. 200% improvement in strength in the case where R ² is 2- (3,4-epoxycyclohexyl) ethyl group, provided test the buckling strength of the concentric ring using a 200% improvement in strength in the case where R ² is a glycidoxypropyl as determined by the strut strength test using a concentric ring, but at the same time only poor moisture resistance (i.e. a 40 to 50% loss) or maintain 50 to 60% strength, in the case of R ² is 2- (3,4 epoxycyclohexyl) ethyl, and the loss of 90 to 100% and the strength retention of 0-10%, where the R group is a glycidoxypropyl group ).

These facts are even more interesting when comparing the marking ability of these coatings (or the possibility of applying labels on these surfaces), as can be seen from the following table:

R ² Marking ability methyl group 0% vinyl group 0 - 10% 2- (3,4-epoxycyclohexyl) ethyl > 60% a glycidoxypropyl group > 60%

However, as noted above, mixtures of one or more hydrolyzed silane-based compositions can be used to form a coating applied to the surface of brittle oxide substrates.

In view of the foregoing, the present invention has achieved substantial application, concurrently and resistance to the developed compositions in which the application improves the strength of the material, with excellent marking effect of moisture.

to which the ability

One such excellent example of the present invention is a composition comprising a hydrolyzed silane-based composition in which R ² represents a methyl group and a group. All these facts to the fact that if made from the individual components forming their desired properties.

2- (3,4-epoxycyclohexyl) ethyl are even more significant with respect to the preparation of this mixture, none of which loses any of the compounds. For example, in the presence of MTMO, i. no. methyltrimethoxysilane, there is no loss of marking ability.

Water. The solutions containing the hydrolyzable silane-based compositions of the present invention are not flammable, especially since there is essentially no organic solvent present in the aqueous solution.

After the coatings have been formed on the brittle oxide substrate, especially after the coatings have been formed on the glass containers, it is preferable to make the layers of the hydrolyzable silane-based composition invisible on the containers. These silane coatings should not be discolored or cured during curing. Hydrolyzed silane-based compositions of the present invention meet the above criteria. In this context, it should be noted that in some industrial applications, the coating formed is required to have a diffuse appearance (i.e., to have some haze or decoration). With the coatings of the present invention, this diffusion appearance requirement can also be met, in which case the temperature of application of the coating to the surface of the brittle oxide substrate is in the range of about 80 ° C to about 100 ° C.

In addition, coloring additives may be added to the aqueous solution containing the hydrolyzed silane-based composition to adjust the color of the coatings. Suitable examples of such dyes include Celestine Blue, Bismark Brown and Eriochrome Black.

In addition to the above, it is possible to use these dyes in the above solutions in order to ascertain the degree of cure and surface coverage of the spraya application. Of course, other substances such as UV blockers can be added to the aqueous solutions and fluorescent agents. With reagents it is possible to achieve an oxide material provided with an object in the dark.

by adding these fluorescent ones, this brittle coated substrate has a luminous property

The coating of the present invention also has the advantage that it has the ability to hide visible abrasion damage on the substrate surface. This is of great value on an industrial scale where flasks are used for reuse, because in the manufacture of these bottles many times a whitish strip is formed around the entire bottle, which is the consequence of damage in many cycles through which the bottles go through during filling.

DETAILED DESCRIPTION OF THE INVENTION

The process of strengthening the brittle oxide substrate, respectively. The procedure for restoring the brittle oxide material, the silane-based composition and the brittle oxide substrate coated according to the present invention will be explained in more detail below with reference to non-limiting examples.

Example 1

According to this example, the soda-lime glass rods were provided with 50 micrometer scratches on their surface, formed by a Vickers diamond digger, which scratches represented the surface bars tested for strength and material defects. Then, these samples were flexural strength, having an average of 56 MPa. The same samples with the same surface defects were then coated by spraying with a 10% w / w solution of vinyltrimethoxysilane (VTMO) in water. This solution contained sufficient sulfuric acid to adjust the pH in the range of 3.0 to 3.4. The samples were then cured by heat treatment for 15 minutes at 200 ° C and tested for flexural strength. The average strength of these samples was increased from 56 MPa to 90 MPa.

Example 2

The procedure of this example was carried out in the same manner as in Example 1. In this example too, the bars were embossed. and a 10% w / v vinyltrimethoxysilane solution, which was acidified as in Example 1, was applied to the bar samples and also contained 0.75% Triton X-102 nonionic surfactant. After curing, these scratch-bar samples increased the strength from 56 MPa to 93 MPa.

Example 3

The procedure of this example was carried out in the same manner as in Example 1 except that the silane used was methyltrimethoxysilane MTMO. The control sample had an average strength of 62 MPa. After coating and curing, the flexural strength of this sample was increased to 96 MPa.

Example 4

The procedure of this example was carried out in the same manner as the procedure of Example 2 using MTMO, i. no. methyltrimethoxysilane. The average strength of the control sample was again 62 MPa, while for the reinforced samples an increase in strength to an average value of 103 MPa was achieved.

Examples 5a6

The procedures of Examples 5 and 6 were analogous to Examples 1 and 2, except that methacryloxypropyltrimethoxysilane MPTMO was used as the silane. In the case of the control samples, according to this embodiment, their strength was 60 MPa.

The specimens were coated and after coating the specimens were thermally cured in the same manner as above, but the specimens were subjected to further UV irradiation to improve their curing. The average strength of the samples according to Example 5 was 126 MPa, while the average strength of the samples according to Example 6 was 124 MPa.

Example 7

In this example, the processing of sheet flat glass samples that have been scored with Vickers diamond digger in such a way as to represent controlled material defects will be illustrated. These controlled defects on the samples were 90 micron scratches. The samples were then coated with a silane solution containing three silanes in the same weight fraction. The total silane concentration was 10% by weight in water, the amount of each silane corresponding to 3.33% by weight. This aqueous solution contained sufficient sulfuric acid to maintain the pH in the range of 3.0 to 3.4. To this aqueous solution was added 0.75% nonionic surfactant Triton X-102 to improve wetting. This solution consisted of glycidoxypropyltrimethoxysilane GPTMO, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane CETMO and methacryloxypropyltrimethoxysilane MPTMO in a 1: 1: 1 ratio.

The strength of the control samples was 45 MPa on average, whereas for the samples treated with the solution at a ratio of 1: 1: 1, the two-stage curing of the coating was carried out for 15 minutes at 125 ° C, followed by curing at temperature. 225 ° C for 10 minutes, an average of 160 MPa, which means about 3.5-fold increase in strength. When using the aforementioned coating composition on these samples, good (label) capability was also noted, although it was contained in MTMO, which generally exhibits poor (labeled) capability.

Marking of this marking mixture

Example 8

The same control samples as in Example 3 were used, consolidated using a solution containing glycidoxypropyltrimethoxysilane GPTMO and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane CETMO in a 1: 1 ratio, the total solution concentration was also 10 % by weight. This solution contained sufficient sulfuric acid to maintain the pH in the range of 3.0 to 3.4. The samples of this example were then thermally cured in the same manner as in Example 3. The strength of the treated samples was increased to 118 MPa and their pre-treatment or initial strength was 45 MPa, which was about 2.6 times increase strength.

Example 9

According to this example, the same defects as described in Example 3 were formed on the walls of the amber glass bottles. The average burst pressure of these samples with defects of 1.9 MPa. The defective flasks were then treated with silane using a solution containing 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane CETMO at a concentration of 10% by weight. The average value of the tear strength was increased to 3.2 MPa in the treated defect control samples, an increase of 68% over the defect control samples.

Example 10

According to this example, standard 0.304 kilogram flasks were engraved in the same manner as in Examples 3 and 9. The average burst pressure of these bottles was 1.9 MPa. The samples were then coated and cured using a 1: 1: 1 solution containing the same ingredients as in Example 7 to form a coating. The average tear strength of these samples was increased from that of the control sample.

1.9 MPa to 3.5 MPa for the treated samples.

Example 11

According to this embodiment, light bottles of 0.304 kilograms were engraved in the same manner as above, and then coated onto the surface of the bottles using a solution containing 10% by weight of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane CETMO, cf. Example 9. The average value at rupture was in scratch control bottles

1.5 MPa. After spray coating and subsequent curing of the coating in the same manner as in Example 3, the average burst pressure was increased to 2.6 MPa.

Example 12

The light bottles, as obtained, weighing 0.304 kilograms were coated with a solution containing 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane CETMO at a concentration of 10% by weight. The tear strength of the control samples was 1.6 MPa. The coated and cured samples had an average burst strength of 3.0 MPa.

Examples 13 to 16

According to these examples, soda-lime glass samples were provided with 50 micrometer scratches on their surface formed by a Vickers diamond digger, which scratches represented surface defects in the material in the same manner as in Example 1. These samples were tested for strength in strut with a concentric ring fixture. The average strength value of these uncoated samples was 69 MPa.

Example 13

An MPTMO suspension, i. no. methacryloxypropyltrimethoxysilane, which was prepared by adding this silane to water acidified to pH 2.5 with a suitable acid, such as sulfuric acid H ₂ SO ₄ , to form an aqueous mixture at a concentration of 10% by weight. Then 0.5% by weight of Triton X-102 surfactant was added to this solution and the composition was aged for 24 hours at room temperature. At this room temperature and after leaving the composition for 24 hours, the oligomers condensed and phase separated to form a suspension. The slurry was applied dropwise to the defect area and the resulting layer was heat cured for 15 minutes at 125 ° C, followed by UV curing. The average strength of this sheet glass was 223 MPa.

Example 14

A 10% w / w suspension of methacryloxypropylmethyldiethoxysilane MPMDEO was prepared in the same manner as described in Example 10, except that a 1% w / w surfactant was used in this suspension. The slurry was then applied dropwise to the sheet glass and the resulting coating was cured for 15 minutes at 125 ° C, followed by curing at 225 ° C for 10 minutes. The strength of these treated sheets of glass was on average 143 MPa.

Example 15

A suspension containing 10% by weight of a 1: 1 mixture of dimethyltetramethoxydisiloxane and methacryloxypropylmethyldiethoxysilane MPMDEO was prepared in the same manner as in Example 10, except that acetic acid was used to adjust the pH to 3.5. and, in addition, no surfactant was used. The sample was then subjected to double curing in the same manner as in Example 14. The sheets of glass treated with the above method had an average strength of 193 MPa.

Example 16

A suspension containing 10% by weight of a 1: 1 mixture of di-tert-butoxydiacethoxysilane (DBDAS) and methacryloxypropylmethyldiethoxysilane (MPMDEO) was prepared in the same manner as in Example 14, except that to adjust the pH sulfuric acid H ₂ SO ₄ was used at 3.5 and an addition of 0.025% by weight of Triton X-102 surfactant was used. The sample was then subjected to two-stage curing, in the same manner as described in Example 12. Samples of this sheet glass treated as above had an average strength of 152 MPa.

Example 17

According to this example, samples of soda-lime glass sheets were provided with 50 micrometer scratches on their surface formed by a Vickers diamond digger, which scratches represented surface defects in the material. Then, the glass sheets were tested for strut strength in a concentric ring fixture with an average strength of 69 MPa. A solution containing 10% by weight of DBAS was then prepared, m.p. no. di-tert-butoxydiacethoxysilane in water, the pH of which was adjusted to 3.5 with acetic acid. This solution was then applied dropwise onto flat sheet glass samples and these samples were then heat cured for 15 minutes at 125 ° C. The strength of the samples thus cured was on average 133 MPa.

Example 18

According to this example, the flat sheet glass samples were treated in the same manner as in Example 17. According to this embodiment, a solution containing 10% by weight of GPTMO, i.e. a solution of 10% by weight, was used. no. glycidoxypropyltrimethoxysilane in water, the pH of this solution was adjusted to 3.5 with sulfuric acid H ₂ SO ₄ . The solution was stored at room temperature for two weeks, then dropped onto the surface defect plates, and then cured so as to first cure for 15 minutes at 125 ° C and then for 10 minutes at 125 ° C. 225 ° C. Sheet glass samples treated as above had an average strength of 219 MPa.

Example 19

According to this example, samples of soda-lime sheet glass were scored with a diamond diamond engraving, with very obvious surface defects. The specimens were then tested for the buckling strength of the concentric ring fixture at an average value of 43 MPa.

An aqueous solution containing 30% by weight of CETMO was then prepared, i. 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, the pH of this aqueous solution was adjusted to

3,5 with sulfuric acid H ₂ SO ₄ . This solution was then added dropwise to the sheet samples with surface defects, after which the coating was cured at 125 ° C for 15 minutes and then at

225 ° C for 10 minutes. The average strength of the treated samples was 61 MPa.

Example 20 of the example was provided on which the board surface was 50 Vickers

According to the soda-lime glass, micrometer scratches, diamond diggers, these scratches represented surface defects in the material. Then, these sheets of glass were tested for strength. in a strut in a concentric ring fixture having an average strength of 69 MPa. A solution containing 10% by weight of N- (3-triethoxysilylpropyl) -4-hydroxybutyramide HBTEO in water was prepared at a pH of 9.5. The solution was then applied dropwise to flat sheet glass samples and the layers were then thermally biphasic cured, first for 15 minutes at 125 ° C and then for 10 minutes at 225 ° C. The strength of the cured samples was after this treatment average 266 MPa.

Example 21

According to this example, the soda-lime glass sheets were provided with 50 micrometer scratches formed by a Vickers diamond digger, which scratches were material defects. These samples were then tested for the buckling strength of the concentric ring fixture and found to have an average strength of 69 MPa.

These sheet glass samples were then coated with a dropwise coating of undiluted MPTMO, i. no. methacryloxypropyltrimethoxysilane, and the applied layer was then cured by passing these samples three times through a UV curing apparatus operating at an energy level

5.3 joules / square centimeter at each pass. The average strength of the treated samples was increased to 104 MPa.

Example 22

The soda-lime glass sheets were engraved in the same manner as in Example 21 and then coated with pyrolytically deposited tin oxide SnO ₂ with a thickness of 15 nm. These samples were then calcined to remove residual stresses. The tin oxide coated controls had a strength of about 83 MPa.

The sample coated with tin dioxide SnO ₂ were then treated with a solution of MTMO, i. no. methyltrimethoxysilane, at a concentration of 10% by weight, was carried out in the same manner as in Examples 3 and 4, thereby increasing their strength to 210 MPa.

Example 23

According to this example, samples of soda-lime glass sheets were provided with approximately 50 micrometer scratches on their surface formed by the Vickers diamond digger, which scratches represented surface defects in the material. Thereafter, these sheets of glass were tested for strut strength in a concentric ring fixture having an average strength of 69 MPa. A solution containing 10% by weight of 3,3-dimethoxypropyltrimethoxysilane (DMPTMO) in water was adjusted to pH 3.5. The solution was allowed to stand for two hours at room temperature, one portion of which was used dropwise to apply to the samples of said defective glass. These samples were then cured for 15 minutes at 125 ° C and then for 10 minutes at 225 ° C. The average strength of the treated samples was 88 MPa. Analysis of the DMPTMO solution by ¹ H nuclear magnetic resonance (NMR) method revealed the presence of only the -CH (OCH ₃ ) ₂ group in the silane triol as a signal at 4.41 (triplet) ppm.

A second portion of the same solution was allowed to stand for 192 hours at room temperature and was then used dropwise to apply to other defective glass samples, after which the coated samples were cured in the same manner as above. The average strength of these flat glass samples was 256 MPa. Analysis of the solution by NMR was found to be present -CH (OH) _(CH3), CH (OH) _2, and -CHO in the silane triol in equilibrium with an approximate abundance of 4: 4: 2 as signals at 4.55 (triplet, ), 4.90 (triplet) and

9.63 (singlet) ppm.

Example 24

According to this embodiment, the bottles were tested on the bottle handling line as follows. Prior to treatment, 120 bottles weighing 0.45 kilograms served as beverage containers tested by the AGR burst pressure test were 2.9 MPa, and were pressure tested. The average strength at which the percentage of bottles which ruptured at a pressure of less than 2.1 MPa was 15%. The treatment of these bottles was carried out by spraying on the bottles a solution of the present invention (in particular a solution containing CETMO, i.e. 2- (3,4-epoxycyclohexyl) ethyl trimethoxysilane), for which a thermal curing of the coating was performed at a temperature 230 ° C or better after applying the coating in a standard cold manner. Then, 120 bottles treated with the above procedure were tested for tear strength in the same manner as above, with an average tear strength of 3.4 MPa, an increase in strength of 16%, with a percentage of bottles, which ruptured at a pressure of less than 2.1 MPa was 6% (decrease by 57%).

Example 25

According to this embodiment, the float glass samples were engraved with a Vickers digger, and then an aqueous solution containing 10% by weight was added dropwise.

3-ureidopropyltrimethoxysilane UPTMO, the pH of this solution was 3.4, and the solution contained 0.05% Triton X-102 surfactant. The prepared samples were then heat treated at 125 ° C for 15 minutes and then at 225 ° C for 10 minutes. The value of the buckling strength of the concentric ring test was as follows: uncoated samples: 66.1 MPa, coated samples: 176 MPa.

Example 26 with ethane.

this

According to this. difference

The strength in the embodiment was repeated as in Example 25 that the silane used was a 1,2-bis (trimethoxysilyl) strut in the concentric ring test in the coating control and cure was an average concentric ring of 136 MPa.

79.8 MPa. strength

After application in test with d 27

According to Example 26, only the reprocessing procedure consisted of 15 minutes. The value of this example was again except that the heat from heating at 125 ° C during average strength was increased from a value of 79.8 coating and curing.

MPa to 164 MPa po

Example 28

The procedure of Example 25 was repeated except that the silane used was 1,2-bis (3-trimethoxysilylpropoxy) ethane BTMOPE, which was prepared by the following procedure.

Allyl bromide (0.7 mol) was added dropwise over 1.5 hours to a stirred mixture containing 0.33 mol of ethylene glycol, 1.25 mol of a 50% aqueous sodium hydroxide solution and 0.025 mol of tributylmethylammonium chloride. The mixture was heated at 80-90 ° C for 12 hours. The mixture was then cooled to 25 ° C while separating the aqueous phase which was drained. The organic phase was diluted with 5 volumes of ethyl ether, washed with saturated sodium chloride solution and dried over sodium sulfate. 1,2-Bis (allyloxy) ethane (BAOE) was then removed by distillation under reduced pressure, boiling at 89-90 ° C at 6.665 kPa.

Then, the mixture containing 0.075 moles of BAOE and 50 microliters of the divinylplatin complex in xylene (Huls America, cat. # PC072) was heated to 85 ° C. Trimethoxysilane (0.160 mol) (Aldrich Chem. Co.) Was added dropwise to the stirred mixture over 2 hours under an inert atmosphere. The mixture was stirred at 85 ° C for 2 hours and then distilled off under reduced pressure. The resulting BTMOPE was collected as a fraction boiling in the range of 135-136 ° C at 33.3 Pa. The strength of the samples determined by the concentric ring test increased from 69.9 MPa (uncoated samples) to 201 MPa (coated and post-cured samples).

Example 29

The procedure of Example 27 was repeated except that the silane of Example 28 was used. The strength of the coated specimens that were cured was an average of 208.0 MPa, while the control strength was 69.9 MPa on average. .

Example 30

A solution containing 5% by weight of CETMO, i. 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane containing 0.025% by weight of Triton X-102 surfactant, to which 0.5% by weight of Celestine Blue (CAS # 1562-90-9) was added. This solution was then sprayed onto 0.45 kilogram beverage bottles using 2.0 grams of solution / bottle. The bottle coatings were then heat treated for 33 seconds in an infrared oven at 700 ° C. The bottles with this coating had a uniform blue coating.

Example 31

According to this example, to a solution containing 10% by weight of CETMO, i. no. 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 0.05% by weight of Triton X-102 surfactant added 1% by weight of Uvinul MS-40 (from BASF Corp.) and 1% by weight of Tinopal CBS-X. This solution was then sprayed onto flat sheet glass samples. These samples were then heat-cured in the same manner as in Example 25. The final coating thickness was 0.9 microns. These samples were then screened for UV transmittance before and after coating and curing. The results are shown in the following table:

sample % throughput at Λ = 340 nm Λ = 380 nm uncoated sample 89 90 sample with cured coating 5 27 Example 32 According to this example she was ready silane mixture as follows. At room temperature were in plastic container connected

one gram of Nafion 50, which is a perfluorinated acidic resin, 2 grams (corresponding to 0.0085 moles) of GPTMO, i.e. glycidoxypropyltrimethoxysilane and 2 grams (0.11 mol) of deionized water. After 15 minutes, additional water was added in an amount

91.9 grams together with 3 grams (0.017 mole) of MTEO (methyltriethoxysilane) and 0.1 grams of Triton X-102 surfactant to give a total of 100 grams of solution.

This formulation (1 hour and 20 days old) was then applied by spraying to a bottle weighing 0.45 kilograms from a simulated one-minute line with a surface temperature of 55 ° C (used AGR line simulator). These bottles were then cured at an average surface temperature of 225 ° C for 30 seconds. For the treated bottles, the tear strength increased by 51% and 50%, respectively. 71% compared to untreated control bottles.

0.6 grams (which had four corners) with 0.6 grams of adhesive were then applied to the surface of the bottles. The glue was then allowed to settle for 16 hours (overnight) at room temperature. These labels were then removed in four attempts (that is, an attempt was made to peel the label manually at each corner until a portion of the label was torn off), and found to have 75-80% label retention (cohesive failure) bottle labels). For comparison, a test was conducted with a 1 hour formulation containing 5 grams of MTEO, i.e. methyltrimethoxysilane and 0.1 grams of Triton X-102 surfactant, applied in the same way to the same type of bottles, with no label retention (no cohesion).

Example 33

In this embodiment, rectangular alumina samples were tested on a three-point bender to determine the ability of the composition of the present invention to solidify the samples. Half of these alumina samples (n = 6) were tested as controls using an Instron 3-point bend setup. The other half of these samples were provided with a layer that was applied by spraying a mixture containing 10% by weight of CETMO, i. no. 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 0.025% by weight of Triton X-102 surfactant and 0.025% by weight of RP-40 (purchased from TH Goldschmidt, Germany), which layer was then thermally cured. in two steps (15 minutes at 125 ° C, followed by curing for 10 minutes at 225 ° C). The control samples showed a strength of 160.65 MPa, while the treated samples had a strength of 194.44 MPa. This result represents a 21% increase in strength.

In view of the results disclosed in U.S. Pat. No. 4,891,241 to Hashimoto et al. Comparative Examples 1, 2 and 3, which are shown in column 25, lines 27-29, where it is stated that no increase in strength was detected. When only silanes are used as a coating composition, the degree of strength increase in the test samples achieved by the process of the invention appears to be quite unexpected. As mentioned above, no additional treatment is used in this process of the invention, as disclosed in Hashimoto et al., Wherein the strength improvement of the treated glass samples has been increased by two or more times compared to the untreated control samples and at the same time they are observed fluctuations in strength relatively small. The strength enhancement achieved according to the present invention is particularly surprising in view of the results reported in the cited United States patent by Hashimoto et al, which are listed in column 5, lines 36 et seq. with siloxanes, it is not sufficient to improve the strength, so it is necessary to use a polymer coating to achieve the desired substrate strengthening.

Various modifications and variations can be made to those skilled in the art by the present invention

It will be apparent to those skilled in the art from the above description and practical examples. The description and examples of the invention are merely exemplary and are not intended to limit the scope of the invention as set forth in the following claims.

Claims (3)

PATENT CLAIMS 1,2-bis (3-trimethoxysilylpropoxy) ethane. 47. A composition suitable as a coating on a brittle oxide material substrate, comprising a mixture 1,2-bis (trimethoxysilyl) ethane. 46. A composition suitable as a coating on a brittle oxide substrate, comprising 1,2-bis (3-trimethoxysilylpropoxy) ethane, 5,6-epoxyhexyltrimethoxysilane (EHTMO), N- (trimethoxysilylpropyl) maleic acid amide, hydrolyzed forms of these compounds and mixtures of these compounds. The frangible container is a container according to claim a glass bottle. a container according to claim 29. Fragile wall thickness of this glass bottle millimeters. 27, characterized by 28, characterized by being in that: 0.1 to 6 The frangible container according to claim further comprising a label on its surface with a transparent co-polymerized crosslinked 31. Fragile container according to the labeling capability of this peel test. 27, characterized by siloxane. of the surface 30, characterized by being greater than about that of the layer by 60% at A frangible container according to the metal oxide layer between the outer layer layer of the co-polymerized claim 32nd further comprising this container and a transparent crosslinked siloxane. 27, characterized in that The frangible container according to claim further comprising a lubricant layer of a co-polymerized crosslinked siloxane. 27, on the surface characterized by the layers of that The frangible container of claim 33, further comprising a label on the surface of the coating indicating lubricants. with that 35. The method of claim 1 wherein said silane composition is a mixture of methyltrimethoxysilane MTMO and hydrolyzed 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane CETMO or a mixture of methyltrimethoxysilane MTMO hydrolyzed 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane CETMO and hydrolyzed glycidoxypropyltrimethoxysilane GPTMO or a mixture of hydrolysed 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane CETMO and hydrolyzed glycidoxypropyltrimethoxysilane GPTMO or a mixture of vinyltrimethoxysilane VTMO and hydrolyzed ketyl hexyl) ethyl 1,2-bis (trimethoxysilyl) ethane, I » 1.5 to 11. The method of claim 17, wherein the silane-based composition is present in said aqueous solution at a concentration ranging from 1% to 99%. 24. The method of claim 17 wherein said silane-based composition is a mixture of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, a surfactant, and acidified water. 25. The method of claim 17, wherein the uncoated strength of the glass container is in the range of 69 kPa to 4,137 MPa. The method of the wall of claim 17, wherein the glass container is in a range of thickness 0.1 to 6 millimeters. 27. A brittle oxide container coated with silane, characterized in that it consists of: (a) a frangible oxide container, (b) a transparent layer of a co-polymerized crosslinked siloxane cured on the surface of the frangible oxide container, wherein the co-polymerized crosslinked siloxane is formed from an aqueous silane-based composition substantially free of organic solvent and the substance is selected from the group consisting of methacryloxypropyltrimethoxysilane (MPTMO), glycidoxypropyltrimethoxysilane (GPTMO), vinyltrimethoxysilane (VTMO), CLAIMS 1. A method for consolidating a brittle oxide substrate comprising the steps of: (a) coating a brittle oxide substrate with an aqueous solution comprising a silane-based composition substantially free of organic solvent, the silane-based composition during hydrolysis in the aqueous solution having the general formula: (oh) ₃ sulfur ² wherein R ² is an organofunctional group, and (b) curing the coating to form a transparent layer on a brittle oxide substrate, wherein the above R group in the silane-based composition is selected such that: (i) substantially improved the strength of said brittle oxide substrate having said cured coating on its surface compared to the strength of the brittle oxide substrate prior to application of said coating; and (ii) said cured coating does not adversely affect the labeling ability this brittle oxide substrate. 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane CETMO. 36. A method for recovering the strength of a brittle oxide substrate comprising the steps of: (a) coating a brittle oxide substrate with an aqueous solution comprising a silane-based composition substantially free of organic solvent, the silane-based composition during hydrolysis in the aqueous solution having the general formula: (OH) ₃ SiR ² wherein R ² is an organofunctional group and (b) curing the coating to form a transparent layer on a brittle oxide substrate, wherein the above R ² group in the silane-based composition is selected such that : (i) achieving a substantial restoration of the strength of said brittle oxide substrate having said cured coating on its surface as compared to the strength of the brittle oxide substrate prior to application of said coating; and (ii) that said cured coating does not adversely affect the labeling capability. this brittle oxide substrate. 37. A method of partially or totally healing a surface defect under stress, comprising the steps of: (a) coating the surface under the effect of stress with an aqueous solution comprising a silane-based composition that is substantially free of organic solvent, the composition based on 51 silane during hydrolysis in this aqueous solution corresponds to the general formula: (OH) ₃ SiR ² wherein R ² is an organofunctional group and (b) curing the coating to form a transparent layer on a brittle oxide substrate, wherein the above R group in the silane-based composition is selected such that: (i) substantially improve the strength of said stressed surface having said cured coating compared to the strength of the stressed surface prior to application of said coating; and (ii) that said cured coating does not adversely affect the labelability of said stressed surface. . 38. The method of claim 37, wherein said stressed surface is a brittle oxide substrate. 39. The method of claim 37, wherein said stressed surface is a glass container. 40. A composition suitable as a coating on a brittle oxide substrate, comprising a mixture of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane CETMO and vinyltrimethoxysilane VTMO. 41. A composition suitable as a coating on a brittle oxide substrate, comprising a mixture of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane CETMO and methyltrimethoxysilane MTMO. 42. A composition suitable as a coating on a brittle oxide substrate, comprising: glycidoxypropyltrimethoxysilane GPTMO, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane CETMO and methyltrimethoxysilane MTMO. 43. A composition suitable as a coating on a brittle oxide substrate, comprising a mixture of glycidoxypropyltrimethoxysilane GPTMO and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane CETMO. 44. A composition suitable as a coating on a brittle oxide material substrate, comprising UPTMO c-3-ureidopropyltrimethoxysilane. r 45. A composition suitable as a coating on a brittle oxide substrate, comprising 2- (3,4-epoxycyhydrolyzovaného 3,3-dimethoxypropyltrimethoxysilane DMPTMO and hydrolyzed 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (CETMO), methyltrimethoxy silane (MTMO), 3,3-dimethoxypropyltrimethoxysilane (DMPTMO), 3-ureidopropyltrimethoxysilane, 2. The method of claim 1, wherein said R ² is selected from the group consisting of glycidoxypropyl, 2- (3,4 epoxycyclohexyl) ethyl, 3,3-dimethoxypropyl, 3-ureidopropyl, hydrolyzed forms of these groups and mixtures thereof. 3. The process of claim 1 wherein said organofunctional moiety is a residue of a hydrolyzable silane. The method of claim 1, wherein the labelability of said brittle oxide substrate is greater than about 50% in a label peel test. 5. The method of claim 1, wherein the labelability of said brittle oxide substrate is greater than about 60% in a label peel test. 6th process according to claim 1 characterized the by that this fragile oxide the material is glass 1. 7th process according to claim 1 characterized the by that during curing said composition on the silane base reacts chemically with fragile oxide substrate. 8th process according to claim 1 characterized the by that this the silane-based composition further comprising at least one of a lubricant, a colorant, a fluorescent agent and / or a UV blocker. The method of claim 1, further comprising the step of applying a metal oxide layer to the brittle oxide substrate performed prior to step (a). 10. A method for consolidating a brittle oxide substrate comprising the steps of: (a) coating a brittle oxide substrate with an aqueous solution comprising a silane-based composition substantially free of organic solvent, the silane-based composition during hydrolysis in the aqueous solution having the general formula: (OH) ₃ SiR ² (b) curing said coating to form a transparent layer on a brittle oxide substrate, wherein the above R ² group in the silane-based composition is (i) brittle such that: substantially improving the strength of the oxide material substrate having said cured coating compared to the oxide material substrate prior to applying said brittle coating surface, and (ii) thereby obtaining substantially improved strength of the oxide material substrate resulting from the application of the cured coating it had a moisture resistance of at least about 50% on this substrate. 11. The method according to claim 10, characterized in that the group R ² is vinyl or methyl. 12. The method of claim 10, wherein the brittle oxide material is glass. The method of claim 10, wherein during curing said silane-based composition chemically reacts with a brittle oxide substrate. Method according to claim 10, characterized in that the silane-based composition further comprises at least one of a lubricant, a colorant, a fluorescent agent and / or a UV blocker. The method of claim 10, further comprising the step of applying a metal oxide layer to the brittle oxide substrate performed prior to step (a). 16. The method of claim 10, wherein said organofunctional moiety is a residue of a hydrolyzable silane. 17. A method of strengthening a glass container comprising the steps of: (a) coating the surface of the glass container with an aqueous solution comprising a silane-based composition substantially free of organic solvent, the silane-based composition during hydrolysis in the aqueous solution having the general formula: (OH) ₃ SiR ² * wherein R ² represents an organofunctional group and ♦ (b) curing the coating to form a transparent layer on the surface of the glass container, wherein the above R ² group in the silane-based composition is selected such that: (i) substantially improved the strength of said glass container having said cured coating on its surface compared to the strength of a brittle oxide substrate prior to said coating; and (ii) said cured coating does not adversely affect the labeling ability of said glass container . 18. The method of claim 17 wherein said organofunctional moiety is a residue of a hydrolyzable silane. 19. The method of claim 17 wherein said n, R is selected from the group consisting of glycidoxypropyl, 2- (3,4-epoxycyclohexyl) ethyl, 3,3-dimethoxypropyl, 3-ureidopropyl, hydrolyzed forms of these groups and mixtures thereof. 20. The method of claim 17, wherein the labelability of said brittle oxide substrate is greater than about 50% in a label peel test. 21. The method of claim 17, wherein the labelability of the frangible oxide substrate is greater than about 60% in a label peel test. The method of claim 17, wherein the pH of said silane-based composition is in the range of 3.3-dimethoxypropyltrimethoxysilane DMPTMO and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane CETMO. Method according to claim 1, characterized in that the composition * The silane-based composition is applied to the brittle oxide material substrate at a temperature in the range of about 80 ° C to about 100 ° C to produce a diffuse appearance during curing.