CA2142904A1 - Brittle oxide substrates strengthened by cross-linkable silanes - 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

~095/00~9 214~ pcT~ss4ln7o34 BRITTLE OXIDE SUBSTF~TES ST~N~
BY CROSS-LINKABLE SILANES

BACKGROUND OF THE INVENTION
This application is a continuation-in-part of U.S.
Serial No. 08/043,980, filed April 7, l9g3, which is a continuation of U.S. Serial No. 07/873,31~ filed April 24, 1992, now abandoned, which is a continuation-in-part of U.S.
Serial No. 07/57S,052, filed August 30, 1990, now abandoned.
This application is also a continuation-in-part of U.S.
Serial No. 07/986,894 filed December 8, 1992, which is a continuation of U.S. Serial No. 07/738,030 filed July 30, 1991, now Ah~n~oned, which wa~ a di~ision of U.S. Serial No.
07/575,052 filed August 30, 1990, now ~h~n~oned.
The present invention relates to a method of strengthen-ing a brittle oxide substrate and also relates to aqueous solutions cont~in; ~g silane-based compositions and polymerized cros -linked siloxane coated brittle oxide substrates. ~or~ particularly, the present invention relates to a method of streng~heni ng or restoring strength to a glass container and the re-qulting polymerized cros~-linked siloxane coated glass COntA ~ nqr .
Brittle materials, such as glass substrates, generally exhibit some mechanical properties, such as, e.g., tensile strength, which re substantially low~r than predicted. This manifestation can arise as the result of such factors as imperfectionq in the structure of a test specimen, or small amounts of impurities in either the body or the surface of an article made of that material. P Gy-QS~iVe zone melting to reform the crystalline structure and floating impurities out SUBSTITUTE SHEET (RULE 26~

_ wo 95to02~9 2 l ~ 2 9 ~ 4 PCT/USg4/07034 ~

of the melted brittle material have been used in the past for brittle metals in an attempt to improve the mechanical prop-erties of the brittle metals. Also, with regard to non-metal brittle materials, multi-layer structures made of the brittle material have been used to improve mechanical properties. In addition, surface treatments of the brittle material have been used to protect the surface from abrasion and to pro~ide a small measure of support to brittle articles.
Glass is intrinsically one of the strongest materials known to man. Theoretically, s~An~rd silicate glasses should be able to support stresses as high as 14 to 20 giga-pascals (2 to 3 million pounds per square inch (psi)). In practice, however, the strengths typically obtained are on the order of 70 megapascals (MPa), about 10,000 psi.
The explanation of the discrepancy between predicted and measured value~ is the existence of surface flaws or cracks.
These flaw~ e~sentially fracture the siloxane network (Si-O-Si), which is the backbone of the glass. This damage to the glas~ acts to concentrate any applied force to the point of causing catastrophic failure of the glass article, typically at much lower stresses than otherwise expected.
While described here for glass, this same theory can be applied to any brittle material not demonstrating significant plastic deformation prior to failure.
In the case of a glass cont~iner, for example, the surface flaws or defects can originate from many sources, ranging from unmelted batch materials to scratches produced ~ 095/~259 21~ 2 9 ~ ~ PCT~S94/07034 by sliding across hard surfaces, including other glass articles. In a typical container-manufacturing facility for example, the glass articles can be heavily damaged by handling from the moment they are formed. Contact with par-ticulates and moisture in the air, other bottles, guiderails and other handling equipment, and the conveyor on which they are transported, can lead to large decreases in the strength of the container due to the flaws produced.
Researchers have long sought a means to alleviate the problems with glass strength. Many modifications to the forming and handling process have led to un~atisfactory increases in the strength because these modifications in handling still leave flaw5 in the surface. For this reason, it has been a goal of researchers to reduce the effect of flaws after they are inevitably formed on the object.
Some approaches to improving the strength of glass include Aratani et al., U.S. Patent No. 4,859,636, wherein metal ion~ in the glass are exchanged with ions of a larger radius to develop a surface compressive stress. Poole et al., U.S. Patent No. 3,743,491, also relates to a surface compre~sive stress, but provides a polymer overcoat to protect the surface from further abrasion. Hashimoto et al., U.S. Patent No. 4l891,241, relate~ to treating the surface of the glaas with a silane coupling agent followed by a polymer coating cont~i ni ng acryloyl and/or methacryloyl groups, followed by irradiation or thermal treatment to polymerize the molecules con~ ing those groups. The '241 patent -W095/~9 21~2 ~ 0 4 PCT~S94/07034 ~

further shows that silanes alone do not strengthen substrates and that acrylates are necessary for any strengthening.
While the patents described above each provide some improvement to the strength of the glass so treated, they are not without shortcomings. Some of these treatments require longer times than available during manufacturing, necessitat-ing off-line processing. There are also concerns related to worker safety and health. In particular, the use and han-dling of organic solvents, as well as the acrylate and methacrylate compounds, are a safety and health concern to the manufacturer.
Therefore, there is an unmet need for a method of strengthening a brittle oxide substrate which addresses the above concerns as well as provide~ accept~ble increases in strength to the brittle oxide substrate. There is also a need for a coated brittle oxide substrate which has a substantially improved strength when compared to a brittle oxide substrate without any coating.
Further, there i~ a need for a method of strengthening a brittle oxide substrate which will also provide acceptable labelability and/or humidity resistance.
In addition, there i~ a need for a polymerized cross-linked siloxane coated brittle oxide substrate wherein the cured coating is transparent.
Additional ob~ects and advantages of the present invention will be set forth in part in the description which follows, and in part will be ob~ious from the description, or 21~2gO. ~
095/~259 PCT~S94/07034 may be learned by practice of the present invention. The objects and advantages of the present invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims.

BRIEF SllMMl~RY OF l~IE PRESD lNVI~;N-l lON
To achieve the objects and in accordance with the pur-poses of the present invention, as embodied and broadly described herein, the present invention relates to a method of strengthening a brittle oxide substrate which includes the following steps. First, the brittle oxide substrate is coated with an aqueous solution contAining a silane-based composition. The aqueous solution cont~i~ing the silane-based composition is substantially absent of any organic solvent. ~urtherl the silsne-based composition upon being hydrolyzed in the aqueous solution ha~ the following formula:

(OH)3siR"
with R~ being an organofunctional group. After coating the aqueous solution cont~ining the hydrolyzed silane-based composition onto the brittle oxide substrate, the coating is cured to form a transparent layer on the brittle oxide sub~trate. Also, R" in the silane-based composition is selected so that (i) the strength of the brittle oxide substrate having the cured coating i~ substantially improved compared to the strength of the brittle oxide substrate prior to the coating step and (--ii) the cured coating does not wo 95,~259 2 ~ ~ 2 9 ~ PCT~S94/07034 ~

interfere with the labelability of the brittle oxide substrate.
The present invention also relates to a method similar to the one described above, except R" is selected so that (i) the strength of the ~rittle oxide substrate ha~ing the cured coating is substantially impro~ed compared to the stren~th of the brittle oxide substrate prior to the coating step and (ii) the substantially improved strength from the cured coating on the brittle oxide substrate has a maintained humidity resistance of at least a~out 50%.
Also, the present invention relates to a polymerized cross-linked siloxane coated brittle oxide container. In particular, the polymerized cross-linked siloxane coated brittle oxide container includes a brittle oxide container and a transparent layer of polymerized cross-linked siloxane preferably cured onto the outer surface o~ the brittle oxide container. The polymerized cross-linked siloxane is formed from a silane-based compo~ition hydrolyzed in an a~ueous solution and sub~tantially lack~ the presence of an organic sol~ent. The hydrolyzed silane-based composition, for example, can be selected from the group consisting of methacryloxypropyltrimethoxysilan~ (MPTMO), glycidoxy-propyltrimethoxysilane (GPTMO), vinyltrimethoxysilane (VTMO), 2-(3,4 epoxycyclohexyl)ethyltrimethoxysilane (CETMO), methyltrimethoxysilane (MTMO), 3,3-dimethoxypropyl-trimethoxysilane (DPTMO), 5,6-epoxyhexyltrimethoxysilane (EHTMO), N-(trimethoxysilylpropyl)-maleic acid amide, ~W095/00259 214 2 9 0 ~ PCT~S94/07034 3-ureidopropyltrimethoxysilane (UPTMO), 1,2-bis(trimethoxy-silyl)ethane ( BTMOE ), 1, 2-bis(3-trimethoxysilylpropoxy)ethane ( BTMOPE ), hydrolyzed forms thereof and mixtures thereof.
The present invention further relates to novel silane-based compositions including, but not limited to, a mixture of vinyltrimethoxysilane and 2-t3,4 epoxycyclohexyl)ethyl-trimethoxysilane; a mixture of methyltrimethoxysilane and 2-(3,4 epoxycyclohexyl)ethyltrimethoxysilane; a mixture of glycidoxypropyltrimethoxysilane, 2-(3,4 epoxycyclo-hexyl)ethyltrimethoxy5ilane, and methyltrimethoxysilane; and a mixture of glycidoxypropyltrimethoxysilane and 2-(3,4 epoxycyclohexyl)e~hyltrimethoxysilane.
The above generally described invention overcomes the difficulties encountered in working with brittle oxide sub-strates such as glass. The method of the present invention drastically and unexpectedly increases or restores the strength of brittle oxide substrates as compared to the strength of the substrate prior to receiving any coating.
Further, the coating~ of the present invention are transparent and safe to use on brittle oxide substrates. se-sides increasing or restoring the strength of the substrate, the coatings of the present invention preferably do not interfere with labelability which has been a problem in the past with coatings on substrates.

i4~4 wos5/oo259 ~ PCT~S94/07034 It is to be understood that both the foregoing general description and the following detailed description are exem-plary and explanatory only and are not restrictive of the present invention, as claimed.

DRTATT~ DESCRIPTION OF THE PRES~NT lNv~LlON
The brittle oxide substrate used in the method of the present invention can be made of any brittle oxide material such as aluminum oxides or aluminates, silicon oxides or silicates, titanium oxides or titanates, germ~n~tes, or glass made from, for instance, the abo~e materials. Further, the brittle oxide substrate can be of any form such as a glass bottle.
The silane-based compositions upon being hydrolyzed in the aqueous solution have the following formula:

(OH)3siR"
wherein R" is an orgsnofunctional group which may or may not hydrolyze in the aqueous solution. This organofuctional group may include residues of hydrolyzable silanes. The selection of R" is further based on the requirement that the resulting aqueous solution containing the hydrolyzed silane-based composition after being coated snd cured on the brittle oxide substrate imparts a substantially improved strength to the brittle oxide substrate and does not interfere with the labelability of the brittle oxide substrats.

-~ O95/002~9 21 ~ 2 9 0 4 PCT~S94/07034 Preferred examples of R" include glycidoxypropyl, 2-(3,4 epoxycyclohexyl)ethyl, 3,3-dimethoxypropyl, 3-ureidopropyl, and hydrolyzed forms thereof.
Accordingly, preferred examples of the hydrolyzed silane-based compositions include hydrolyzed glycidoxypropyl-trimethoxysilane, hydrolyzed 2-(3,4 epoxycyclohexyl)ethyl-trimethoxysilane, hydrolyzed 3-ureidopropyltrimethoxysilane, and hydrolyzed 3,3-dimethoxypropyltrimethoxysilane.
The coating applied to the brittle oxide substrate can also be a mixture of one or more hydrolyzed silane-based com-positions. The mixture of two or more hydrolyzed silane-based composition5 is especially advantageous when it is known that one hydrolyzed silane-based composition pro~ides excellent labelability and another hydrolyzed silane-based composition provides excellent strength enhancing properties.
Thus, a mixture would provide the desired balance of properties, that is, a coating which provides i~ oved stren~th and which does not interfere with labelability. For instance, a mixture of hydrolyzed CETMO and methyltrimethoxy-silane (MTMO) can be used to obtain this balance of properties.
Other examples of hydrolyzed silane-based compositions which can be used in mixtures of one or more hydrolyzed silane-based compositions include hydrolyzed methacryloxy-propyltrimethoxysilane, hydrolyzed 3-ureidopropyltri-methoxysilane, hydrolyzed 1-2-bis(trimethoxysilyl)ethane, hydrolyzed 1,2-bis(3-trimethoxysilylpropoxy)ethane, _ g _ W095/00259 2 ~29Q PCT~S94/07034 hydrolyzed 5,6-epoxyhexyltrimethoxysilane, hydrolyzed N-(trimethoxysilylpropyl)-maleic acid amide, hydrolyzed dimethyltetramethoxydisiloxane, and hydrolyzed N-(3-triethoxysilylpropyl)4-hydroxybutyramide tHBTEO). These compositions, for instance, can be used in a mixture with hydrolyzed CETMO and/or hydrolyzed GPTMO and/or hydrolyzed DPTMO. Generally, the silane-based compositions used in a mixture can be added in equal proportions. O course, if stronger labelability properties are desired, a greater proportion of hydrolyzed CETMO, hydrolyzed GPTMO, or hydrolyzed DPTMO, for instance, would be added. Further, any of the compositions described herein can be used alone to substantially improve the strength of a brittle oxide substrate, if labelability is not a concern.
Unless stated otherwise, the silane-based compositions provided as specific examples are commercially available from one or more of the following sources, Union Carbide, Dow Corning, Hul~ America and PCR, Inc.
While the coatings of the present invention can be mix-ture~ of one or more hydrolyzed silane-based compositions, separate coating3 of hydrolyzed silane-based compo~itions can be applied to a surface of a brittle oxide substrate. For example, a coating of CETMO can be applied to a surface of a brittle oxide substrate and then while the CETMO coating is still wet or dry or after curing the first coating, a second coating, another CETMO coating or a different coating (e.g.
MPTM0), can be applied.

21~9~4 095/~259 PCT~S94/07034 Any number of such consecutive separate coatings can be applied in this manner. Further, a surfactant can be applied in this manner, namely, coating a brittle oxide surface with a surfactant before and/or after coating the surface with a hydrolyzed silane-based composition(s). Even coatings like that of Hashimoto et al. (U.S. Patent No. 4,891,241) can be applied after applying the coatings of the present invention.
It is to be understood that by applying the coating(s) of the present invention to a surface of a brittle oxide sub-strate, this also includes applying the coating( 5 ) of the present invention to any previous coating on the brittle ox-ide substrate. An example of a previous coating would include hot-end coatings, typically applied in the industry.
The silane-based compositions used in the method of the present invention can be present in the aqueous solution at an average concentration from about 1% to about 99% by weight in water or aqueou$ solution, preferably from about 1% to about 30% and most preferably from about 2% to about 10%.
With regard to the aqueous ~olution contA i n i ng a hydrolyzed silane-based compo~ition, the amount of water added to the silane-based composition to prepare the aqueous solution of the present invention is based on the concentration of the resulting aqueous solution desired. A
more dilute hydrolyzed silane-ba~ed composition would simply mean that more aqueous solution contAining the hydrolyzed silane-based composition would need to be coated onto the -W095/00259 ~ ~ 4~g 0 ~ PCT~Sg4/07034 ~

brittle oxide substrate to achieve the substantially improved strength in the brittle oxide substrate.
As used herein, the term solution includes chemical solutions, suspensions, emulsions, and mixtures, any of which may exhibit complete or incomplete intenm;xing.
The aqueous solution containing the hydrolyzed silane-ba~ed composition can be prepared all at once, me~ing the silane-ba~ed composition is added to water at the manufactur-ing facility. Alternatively, the hydroly%ed silane-based composition can be prepared as a neat or concentrate and, at the user site, can be diluted with water in order to prepare the aqueous solution cont~i n i ng the hydrolyzed silane-based composition for actual coating onto the brittle oxide sub-strate.
Further, the aqueous solution contAi~ing the hydrolyzed silane-based composition of the present invention is substan-tially free of an organic solvent, meaning no organic solvent is intentionally added to the ~olution. Some organic compounds, however, may be pre~ent a~ an impurity and/or by-product of the silane-based composition reacting with water or the aqueou~ solution reacting upon curing. Further, some of tha commercially a~ailable silane-based compounds may contain organic solvents which are diluted upon being introduced into the aqueous solution so that the percent solvent is approximately equal to or less than the silane concentration in the aqueous solution. One example is UPTMO.

~ 095/00259 21~ 2 9 0 4 PCT~S94/07034 Of course, it is known that the addition of a solvent can increase the stability of a solution.
The following reaction scheme sets forth the two reactions which are believed to occur in the preparation and application of the aqueous solution containing the hydrolyzed silane-based composition.

( R ' O ) 3SiR + 3H20 c----> ( OH ) 3SiR" + 3R ' OH ----> Si-O-Si coating In this reaction, the trialkoxy silane reacts in water to form the trisilanol in solution. The trisilanol in solution can contain oligomers. Then, the trisilanol in solution condenses to form the polymerized cross-linked siloxane (Si-O-Si) coating upon curing. This siloxane (Si-O-Si) coating generally contains an organic substituent(s) such as the R" group(s).
In this reaction scheme, R'O can be any group that is hydrolyzable. The following R' groups best meet this o criteria, -CH3, -C2Hs, and -CCH3. However, other groups which meet thi~ criteria are well known to those skilled in the art.
The R group is an organofunctional group that may hydro-lyze during the hydrolysis reaction to form the R" group.
This organofunctional group can be a residue of a hydrolyzable silane. Following the hydroiysis reaction and if the R group is hydrolyzable, the R' group contains at least one hydroxyl (OH) group. If the R group is not WOg5/00259 PCT~S94/07034 2~ 4~9~ ~
hydrolyzable, then R and R' would be the same, for instance, when R is vinyl or methyl. In general, the R group in the above reaction scheme is preferably selected so that the silane-based compositions of the present invention provide the appropriate balance between improved or restored strength and labelability. Accordingly, preferred examples of the R
group include glycidoxypropyl, 2-(3,4 epoxycyclohexyl)ethyl~
and 3,3-dimethoxypropyl. Further, pre~erred examples of the R~' group would be hydrolyzed ~ersions of these preferred R
compounds.
The above-described reaction scheme by no means is mean~
to limit the manner in which the aqueous solution cont~; n; ~g the silane-based composition is prepared. Instead of start-ing with trialkoxy silanes, one can ~ust as easily begin with any hydroLyzable silane. For instance, halide silanes such as substituted trichlorosilanes.
As noted above, upon hydrolysis, the R group can become hydroxyl (OH) cont~; n ing a~ the R" group. For example, CETMO
and GPTMO wh$ch both have an epoxy ring in the R group, upon hydrolysis in the aqueous solution, will result in a dihydroxy group by the opening of the epoxide ring while the rest of tha R" group r~m~;~s hydrophobic. Thus, the R~ group has a balance of hydrophilic (provided by the OH groups) and hydrophobic properties. The hydrophilic properties in the R
group particularly improve the strength and the labelability.
A surfactant can be added to the aqueous solution cont~ining the hydrolyzed silane-based composition to improve 095/00259 ~1~ 2 9 o ~ PCT~S94/07034 coverage of the aqueous solution containing the hydrolyzed silane-based composition around the brittle oxide substrate surface which results in a greater strengthening of the brittle oxide substrate and better appearance. Generally, only a small amount of surfactant is added to allow the silane coating to spread out better on the brittle oxide substrate. Non-ionic surfactants have been especially useful in this regard. One example of such a surfactant is commercially available Triton X-102 (obtained from Union Carbide) which is octylphenoxy polyethoxy ethanol. Gener-ally, from about 0.001 wt.~ to about 1.0 wt.~ tbased on total weight of solution) of a surfactant can be added.
Preferably, from about 0.01 wt.% to about 0.05 wt.% (based on total weight of solution) of a surfactant i8 added.
Those skilled in the art will realize that other com-pounds can be added to the aqueou~ solution containing the silane-based composition for the purpose of improving the wetting, or providing other effects such as U.V. stability or control of rheological propertie~.
The pH of the aqueous solution contAining the silane-based compositions are generally ad~usted to the range of about 1.5 to about 12 with the pH usually being ad~usted in the preferred rango of about 2 to about 4 because the aqueous solutions during testing have shown to be most stable at this pH range. Generally, the pH of the aqueous solutions con-taining the hydrolyzed s~i~ane-based compositions is adjusted based upon the R' group selected. The pH of the aqueous wo 95,~259 - C A 2 1 4 2 9 0 4 PCT~S94/07034 ~

solutions can be adjusted to the desired pH by the addition of a basic or acidic compound.
The aqueous solution containing the hydrolyzed silane-based composition can be affected by aging which can eventually result in a decrease in the amount of strengthening improvement of the brittle oxide substrate.
Interestingly, slight aging can, in certain circumstances, be beneficial; for instance GPTMO. However, with further aging, there is an eventual decrease in properties. The shelf life of the aqueous solutions containing the hydrolyzed silane-based compositions is based on a composition by composition basis. For instance, with respect to an aqueous solution wherein the hydrolyzed silane-based composition is hydrolyzed CETMO, a shelf life of at least 100 days is possible without any effect on the ability to substantially improve the strength of the brittle oxide substrate.
The aqueous solution cont~ining the hydrolyzed silane-based composition is deposited or coated onto the substrate surface by spraying, dripping, dipping, painting, or any other techniques suited to the application of liquids, vapor~, or aerosol~. Preferably, the aqueous solution cont~ning the hydrolyzed silane-based composition is applied a~ a spray in an added or substituted spray step in the present commercial production and treatment of glass containers such as bottles, discussed below, using conventional spray equipment.

095/00259 21~ 4 PCT~S94/07034 The coating of the present invention can be applied directly onto any surface (e.g., internal, external, or portions thereof) of the brittle oxide substrate or can be applied to an exterior layer the composition of which is different from that of the brittle oxide substrate. For instance, the coating of the present invention can be applied to a tin-, titanium-, silicon-, or other metal-oxide layer or mixtures of such materials and still be effective in strengthening the brittle oxide substrate.
Typically, in the production of glass containers such as bottles, the bottles, which are on a conveyor line pass through 1) a hot end coating hood wherein a layer of an inorganic tin is applied, such 8S tin oxide; 2) an annealing lehr; and 3) a lubricant spray step. By using the method of the present invention, the application of the aqueous solution cont~ining the silane-based solution preferably occurs after the glass bottles exit the annealing lehr and would be considered a cold-end coating.
The aqueous solution cont~i~;ng the silane-based composition can be applied at any temperature below the boiling point of the aqueous solution, but generally is applied at or near room temperature.
Further, while the aqueous solution cont~i n ing the silane-based composition can be applied at any brittle oxide (e.g. bottle) surface temperature abo~e the freezing point of the aqueous solution, a brittle oxide surface temperature WO95/0025g ~ ~ PCT~S91/07034 from about 20 to about 200C is preferred, and a surface temperature from about 50 to about 60C is most preferred.
Once the brittle oxide substrates (e.g. glass bottles) are coated with the aqueous solution containing the silane-based composition, the coated brittle oxide substrates enter a curing unit, such as a curing oven, wherein the surfaces of brittle oxide substrates usually obtain a temperature of at least about 230C. Certainly, effective curing with surface temperatures lower than 230C are possible with certain silane-based coatings such as with BTMOE. Once this surface temperature is obtained effective curing occurs. For instance, the surface temperature can be held at the at least about 230C for about 30 second5. The temperatures used during curing need to be high enough to cure the coated brittle oxide substrates without browning the coating. The temperature range for effective curing is based, in part, on the R group selected. For instance, for hydrolyzed CETMO, generally, temperatures below about 200C provide marginal results and temperatures above about 350C result in the charring of the coating.
The cure step in the method of the present invention can be effected by the application of energy of any source at a magnitude sufficient to el--ova, e.g., water or other non-coating reaction products from the surface of the treated brittle oxide substrate, provided that such application is not deleterious to either the brittle oxide substrate or the coating material. The curing step, being a combined function WOg5/~25s ~ 9 0 4 PCT~S94/07034 of energy and time, can include a low magnitude of energy for a relatively long time, or the reverse, an application of a high magnitude of energy limited as noted hereinabove, for a relatively short period of time. Examples of such energy sources include microwave, infrared, ultraviolet ( W), irradiation or exposure to ambient or elevated temperatures, such as in an electric or gas heating oven, at, above or below atmospheric pressure, or a combination of such conditions.
After exiting the curing step, a conventional lubricant spray step, mentioned above, can be used to add a polymer coating such as polyethylene to the brittle oxide substrates for purposes of lubricity. The coatings of the present invention permit the adhesion of the lubricant to be at least as good as the adhesion of the lubricant to the hot end coating discussed above.
With the coating~ of the present invention, it is possible to obtain sufficient lubricity in the brittle oxide substrate in order to avoid any lubricant spray step, especially with regard to bottle manufacturing.
Strength, as described herein, refers to the m-ximllm load a specimen can withstand prior to catastrophic failure (and destruction of thQ article). There are numerous methods for measuring failure strength dependent upon sample geometry and article application. These include bending strength, vertical load, burst pressure, concentric ring strength, and impact testing.

W095/~25g ~ Q ~ PCT~S94/07034 The method of the present invention actually strengthens the brittle oxide substrate. As stated in the background, theoretically, all brittle oxide substrates, especially glass, are damaged in some way by minute flaws or by the presence of small impurities. Since the brittle oxide substrates theoretically should have a much higher strength, one could characterize the present invention as a method of restoring strength to a brittle oxide substrate since the method of the present invention is providing a degree of strength to the brittle oxide substrate which is closer to its theoretical strength.
One way of measuring the actual strength of the brittle oxide substrate with and without the coating of the aqueous solution contA i n i ng a hydrolyzed silane-based composition is by a concentric ring strength test as described in the Journal of Strain Analysis, Vol. 19, No. 3 (1984) and the Journal of Non-Crystalline Solids, 38 & 39, pp. 419-424 (1980), which is a test commonly recognized by those skilled in the art.
Another way of measuring the st~ength is by a burst pressur2 strength test as de~cribed in ASTM Test C-147 using a ramp pressure tester (obtAine~ from AGR, Intl. Literature), which is a test also commonly recognized by those skilled in the art.
A further way of measuring the strength is by an impact strength test as described in the instructions which are provided with the AGR Impact Tester. This test is industry W095/~25g 21 ~ ~ 9 D ~ PCT~S94/07034 recognized and is accomplished with the use of an AGR impac~
tester unit obtained from AGR, Int'l., Butler, PA. The strength test is commonly recognized by those skilled in the art as well.
As noted, the application of the a~ueous solution cont~ini~g the hydrolyzed silane-based composition of the present invention substantially improves the strength of a brittle oxide substrate. The substantial strength improvement is demonstrated by the concentric ring strength, burst pressure strength, or impact strength improving at least about 10%. Preferably the strength imp~ov~l~.ent is at least 20%.
Those skilled in the art will recognize that by increasing the strength of a brittle oxide substrate or article, e.g., glass, a les~er amount of oxide substrate is needed to form an article of substantially equivalent strength and general mechanical performance. Thus, in the specific ca~e of a glas~ container such a~ a bottle, for instance, the bottle can be lighter in weight than its untreated counterpart. Furthermore, incressing the strength leads to less failures of the product (e.g., less breakage during commercial use.
It is theorized that the polymerized cross-linked siloxane linkage occurs within the coating, as well as between the coating and the brittle oxide substrate surface.
The coating, after bonding to the surface, can act to heal cracks in the surfaces by forming an Si-O-Si network across 2~ o ~
WO95/~259 PCT~S94/07034 the flaw surfaces. The formation of the siloxane bonds in the region of the flaws acts to provide an increase in the breaking stress of the article.
For a coating to actually restore or increase strength to a sample which has previously been damaged, the effect of stress-concentrating flaws on the tension-bearing surface must be mi~imized. This requires a partial or complete healing of the flaws in the tension-bearing surface. For a glass container being pressure-tested, the surface experiencing tension is pred~inA~tly the external surface of the bottle since the walls actually bow outward as pressure is increa~ed. In general, that external surface will be the one which develops a convex curvature during loading.
It is possible, however, to increase the load required for impact failure of a sample without necessarily restoring strength to the substrate. This technique make~ use of a coating on the surface being impacted, rather than the side experiencing the tensile strength. (Impact generally induces a tensile stress in the interior surface of a container.) The mechanism in this csse relies upon the ability of the coating to absorb the energy of the impact such that the energy i~ not transmitted to the substrate in the form of a flexural stres~. The measured impact load for failure will be increased, but the flexural strength of the ob~ect will not have changed.
Commercially produced glass containers are typically coated with a metal-oxide film shortly after fabrication, W095/~9 214 2 9 0 4 PCT~S94/07034 using chemical vapor deposition; this is referred to as a hot-end coating (HEC). Generally, this coating will be tin oxide, but can be titanium or other metal oxide, and can have other ingredients to enhance physical properties, e.g., electrical conductivity. This coating is typically about 50 to 125 Angstroms thick. The present invention restores or increases the strength of damaged glass, whether or not a previously deposited HEC exist~ on the surface.
With respect to labelability of the brittle oxide substrate, it is to be under5tood that certain cured hydrolyzed silane based coatings of the present invention do not interfere with this labelability as discussed previously.
Labelability is measured by the following label peel test.
A paper label with four corners and having an area of about 6 square inches is used. The label is weighed prior to the application of a ca~ein type adhesive identified as 4242 available from National Starch. About 0.6 grams of the casein type adhesive is applied to the back of the label (opposite side) and spread on the label by rolling with a 5 mm glass rod or similarly shaped ob~ect to uniformly spread the adhesive on the label. The label is pressed on a surface of a brittle oxide substrate and allowed to dry for a minimum of two hours at room temperature. The label i5 peeled by hand at every corner until a portion of the label tears from every corner of the substrate. A coating is considered to have acceptable labelability for purposes of the present wo 95/002~9 ~ ~ 42 9 ~ ~ PCT~S94/07034 invention if greater than about 50% by weight of the label r~m~ins on the surface of the brittle oxide substrate.
Preferably, the labelability (based on the ~ by weight of the label remaining on the surface of the brittle oxide substrate) of the coated brittle oxide substrates of the present invention is greater than about 60%, most preferably greater than about 70% by weight.
The substantially improved strength from the cured coating on the brittle oxide substrates can also exhibit a maintained resistance to the detrimental effects of humidity.
In fact, a humidity resistance test provides an acceptable way of determ; ni ng how well the coatings of the present invention allow a coated brittle oxide surface to retain the improved or restored strength. The excellent and maintained resistance to humidity which can be exhibited by the silane-based coatings of the present invention is generally dependent upon the R" group. One way to determine the effect of humidity on the coatings of the present invention is to compare the strength of coated brittle oxide substrate when the cured coating on the substrate is le~s than 3 hours ~ld at relative humidity which generally is approximately 40~, with the strength of the same coated brittle oxide substrate sub~ected to a 90% humidity for a period of 30 days. In such a test, the humidity resistance of the cured coatings of the present invention applied to the brittle oxide substrates has only about a 50%, preferably only about 20-30%, most preferably 0-10%, change in strength which is excellent, W095/002~9 214 2 9. 0~ PCT~S94/07034 especially for purposes of glass bottles subjected to high humidity environments such as in the southern United States.
Interestingly, not all of the hydrolyzed silane-based coatings provide excellent humidity resistance once coated onto a brittle oxide substrate. For instance, and as a comparison, when a hydrolyzed silane-based composition, wherein R" is vinyl or methyl, is coated onto a brittle oxide substrate and cured, the strength of the substrate substantially improves, (e.g., 110% imp uv~ cnt (concentric ring test) when R" i5 vinyl and 200% improvement (concentric ring test) when R" is methyl) and excellent humidity resistance is obtained (e.g., 0% loss (100% strength maintained) when R" is vinyl and 0% loss (100% strength maintained) when R" is methyl); however, when a hydrolyzed silane-based composition, wherein R" is 2-(3,4 epoxycyclohexyl)ethyl or glycidoxypropyl, i8 coated onto a brittle oxide sub~trate and cured, while the strength of the coated substrate ~ubstantially improve~ (e.g., 200%
impLov~l,.ent (concentric ring te~t) when R" is 2-(3,4 epoxycyclohexyl)ethyl and 200% improvement (concentric ring test) when R~ i~ glycidoxypropyl), only fair humidity resistance i~ obtained (e.g., 40-50% lo~s (50-60% strength maint~ine~) when R" i~ 2-(3,4 epoxycyclohexyl)ethyl and 90-100% loss (0-10% strength maintained) when R~
glycidoxypropyl).
This is all the more interesting when the labelability of these coatings are compared:

W095/00259 ~ 90 ~ PCT~S94/07034 R LabelabilitY

methyl o~
vinyl 0-10%
2(3,4 epoxycyclohexyl)ethyl > 60%
glycidoxypropyl > 60~

However, as stated earlier, the coating applied to the brittle oxide substrate can be a mixture of one or more hy-drolyzed silane-based compositions.
Thus, the present inventors have discovered mixtures which provide substantially improved strength along with excellent labelability and humidity resistance. A mixture of a hydrolyzed silane-based composition wherein R" is methyl and 2-(3,4 e~o~y~yclohexyl)ethyl is one excellent example.
It is all the more remarkable that when such a mixture is made, none of the individual components in the mixture detract irom any of the desired propertie~. For instance, the presence of MTMO does not detract from the labelability properties.
The aqueous solutions cont~;ni ng the hydrolyzed silane-based compositions of the present invention are non-flammable especially in view of the fact that there is a substantial absence of organic solvent~ in the aqueous solution.
When coating brittle oxide substrates, especially glass containers, it is preferred that the hydrolyzed silane-based composition is not visible on the container. The silane coating should not discolor or become textured upon curins.
The hydrolyzed silane-based compositions of the present invention meet this criteria. It is noted that in some ~o 9s,~25g 2 I i 2 9 0 4 PCT~S94/07034 commercial applications, a coating which is diffused (somehaze or fresco) is desired. The coatings of the present invention are also capable of this diffused appearance by using an application temperature (e.g. brittle oxide substrate surface temperature) of from about 80C to about 100C .
Further, color dyes can ~e added to the aqueous solution in order to make colored coatings. Examples of suitable dyes include Celestine blue, Bismark brown, and Eriochrome black.
Further, dyes can be used in the aqueous solution for indicating the degree of cure and spray coverage. In addition, other components can be included in the ~queous solution, such as W blockers and fluorescing agents.
Including a fluorescing agent will permit the coated brittle oxide substrates to have a "glow-in-the-dark~ property.
The coatings of the present invention also advantageously have the ability to hide visible scuff damage to a substrate surface. This is particularly desirable in the refillable bottle industry wherein bottles eventually develop a whitened track around the bottle from numerous cycles through a filling line.
The present invention will be further clarified by the following examples, which are intended to be purely exemplary of the present invention.
Exam~le 1 In this example, soda-lime glass rods were indented with a Vickers diamond to produce approximately 50-micro-meter W095/00259 ~ 9 PCT~S94/07034 .

(um) flaws in the surface. These rod samples were tested to failure in bending, and had average strengths of 56 MPa.
Samples with identical flaw5 were spray-coated with a solution of 10 percent by weight (wt.%) of vinyl trimethoxysilane (VTMO) in water. The solution contained enough sulfuric acid to adjust the pH to between 3.0 and 3.4.
The samples were thereafter heat-treated for 15 minutes (min.) at 200C, and tested in bending. The average strength of these samples increased from 56 MPa to 90 MPa.
ExamPle 2 Example 2 is a modification of Example 1. In this example, the samples were again indented rods, and the solution was 10 wt.% VTMO, acidified as set forth in Example 1. This solution also contained 0.75 wt.% of the nonionic surfactant Triton X-102. After curing, the indented samples increased in strength from 56 MPa to 93 MPa.
ExamPle 3 Example 3 is identical to Exampl~ 1, with the exception that the silane used was methyltrimethoxysilane (MTMO). The control samples had an average strength of 62 MPa. Upon coating and curing, the bend strength was increased to 96 MPa.
ExamPle 4 Example 4 is a duplication of Example 2, using MTMO.
The a~erage control strengths were again 62 MPa, but the strengthened samples averaged 103 MP8.

~ o 9~,002~9 2 1 4 ~9 0~ PCT~S94/07034 ExamPles 5 and 6 Examples 5 and 6 are duplicates of Examples 1 and 2, respectively, with the exception that the silane used was methacryloxypropyltrimethoxysilane (MPTMO). For these samples, the average control strength was 60 MPa.
Once coated, these samples were thermally cured as described above, but were also subjected to an additional W
irradiation in order to enhance the curing. The strengthened samples for Example 5 attained an average strength of 126 MPa, while those for Example 6 reached 124 MPa.
Exam~le 7 This example illustrates the treatment of flat-glass samples which were indented with a Vickers diamond to form a controlled flaw. Samples were indented such that 90-um flaws were produced. These samples were coated with a silane solution consisting of three silanes in the same weight proportion. The overall silane concentration was 10 wt.% in water, while the amount of each silane was about 3.33 wt.%.
The solution contained enough sulfuric acid to bring the pH
to between 3.0 and 3.4. A nonionic surfactant, Triton X-102, was added in the amount of 0.75 wt.% in order to increase wetting. The 1:1:1 solution consisted of glycidoxypropyltrimethoxysilane (GPTMO), 2-(3,4 epoxycyclohexyl)ethyltrimethoxysilane (CETMO), and MTMO.
The control strengths were 45 MPa, while the samples treated with the l:1:1 solution were 160 MPa after a two-step cure consisting of a 15-minute cure at 125C, followed by a W095/00259 2 i ~9 Q 4 PCT~S94/07034 cure at 225C for 10 minutes, an increase in strength of about 3.5 times. Good labelability was also found for this mixture e~en though MTM0 (generally exhibiting poor labelability by itself) was present in the formulation.
Exam~le 8 The same control samples as described in Example 3 were strengthened using a 1:1 solution of GPTM0 and CETM0, also in a 10 wt.~ total concentration~ The solution contained enough sulfuric acid to bring the pH to between 3.0 and 3.4. These samples underwent the same heat treatment described in Example 3. The strength of the treated samples was increased to 118 MPa from the starting strength of 45 MPa, for an increase in strength of about 2.6 time~.
Exam~le 9 The same flaws described in Example 3 were applied to the sidewalls of amber bottles. The a~erage burst pressure of these flawed containers was 1.9 MPa. The flawed bottles were then silane-treated, using a 10 wt.~ solution of CETM0 and the same cure procedure described in Example 3. The average burst strength of the traated control-flawed samples was increased to 3.2 ~Pa, an increa~e of 68~ o~er the flawed control samples.

ExamPle 1 0 StAnA~rd 12-ounce (oz.) beer bottles were indented as described in Examples 3 and 9. The average burst pressure of these flawed containers was 1.9 MPa. Samples were coated and cured with the 1:1:1 solution as described in Example 7. The WOg5/~25g 21 ~ 2 g a q PCT~S94/07034 average burst strength was increased from the control value of 1.9 MPa to 3.5 MPa for the treated samples.
ExamPle 11.
Lightweight 12-oz. bottles were indented as set forth above, and coated with the lO~ CETMO solution described in Example 9. The average burst pressure for the indented controls was 1.5 MPa. Upon spray-coating, and subsequent curing as set forth in Example 3, the average burst pressure of the bottles was increased to 2.6 MPa.
Exam~le 12 Lightweight 12-oz. bottles were coated in the as-received state with a 10 wt.% solution of CETMO. The burst 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 throu~h 16 In these examples, soda-lime flat-glass specimens were indented with a Vickers ~ A -nd tip to produce the 50-um flaws on the surface as described in Example l. These samples were tested with a concentric-ring fixture. The mean strength of these uncoated samples was 69 MPa.
ExamPle 13 A suspension of MPTMO was prepared by adding the silane to water acidified to a pH of 2.5 with a suitable acid, e.g., H2SO4, to give a 10 wt.% mixture. 0.5 wt.% Triton X-102 was added, and the composition aged for 24 hours at room temperature. The condensing oligomers phase-separated at room temperature after 24 hours, forming a suspension. l'his WO95/00259 2 1 4 ~ 9 q ~ PCT~S94/07034 suspension was applied by drip-coating over the flaw region and heat-treating for 15 min. at 125C, followed by an W
cure. The mean flat-glass strengths were 223 MPa.
ExamPle 14 A 10 wt.~ suspension of methacryloxypropylmethyldiethoxy-silane (MPMDEO) was prepared using the same procedure as described in Example 10, but using the surfactant at a 1 wt.% level. The suspension was drip-coated on flat glass and the coating was cured for 15 min. at 125C followed by a cure at 225C for 10 min. The treated flat-glass specimens had mean strengths of 143 MPa.

ExamPle 15 A 10 wt.% suspension contAining a 1:1 wt. mixture of dimethyltetramethoxydisiloxane and MPMDEO was prepared as described in Example 10, except that acetic acid was used to ad~ust the pH to 3.5, and no surfactant wa~ added. The sample received a dual cure as de~cribed in Example 14. The treated flat-glass specimens had mean strengths of 193 MPa.
ExamPle 16 A 10 wt.% suspension cont~i ni n~ a 1:1 wt. mixture of di-tert.-butoxydiacetoxysilane (DBDAS) and MPMDEO was prepared as described in Example 14, except that H2SO~ was used to ad~ust the pH to 3.5, and 0.025 wt.% Triton X-102 was added. The sample received a dual cure as described in Example 12. The treated flat-glass specimens had mean strengths of 152 MPa.

~ 095/~259 21 4-2 9 0 4 PCT~S94/07034 ExamPle 17 In this example, flat soda-lime glass specimens were indented with a Vickers diamond to produce approximately 50-um flaws. The samples were tested with a concentric-ring fixture, and had average strengths of 69 MPa. A solution of 10 wt.% of DBDAS in water was adjusted with acetic acid to a pH of 3.5. The solution was drip-coated onto a flat glass specimen, and the article thermally cured for 15 min. at 125C. The cured specimens had a mean strength of 133 MPa.
ExamPle 18 Flat-glass specimens were treated as in Example 17. The pH of a solution of 10 wt.% GPTMO in water was ad~usted with H2SO4 to 3.5. The solution was stored at room temperature for two weeks, after which the flawed slides were drip-coated with the solution and cured first at 125C for 15 min. and then at 225C for 10 min. The mean strength was 219 MPa.

ExamPle 1 9 Flat soda-lime-glass specimens were indented with a round diamond tip to produce a readily ~isible impact flaw.
The specimens had mean concentric-ring strengths of 43 MPa.
The pH of an aqueous solution of 30 wt.% CETMO in water was ad~usted with H2SO4 to 3.5. The solution wa~ drip-coated onto the flawed slide and thermally cured at 125C for 15 min. and then at 225C for lO min. The mean strength was 61 MPa.

W095/002S9 2~9 ~ PCT~S94/07034 Example 20 Soda-lime glass f lat-glass specimens were indented with a Vickers diamond to produce approximately 50-um f laws.
These samples were tested with a concentric-ring f ixture, and had average strengths of 69 MPa. A solution of 10 wt.
N-(3-triethoxysilylpropyl)-4-hydroxybutyramide (HBTEO) was prepared in water and allowed to stand for 30 days; the pH
was 9.5. The flawed slides were then drip-coated with the solution, and dual-cured at 125C for 15 min., followed by 225C for 10 min. The tested mean strength after treatment was 266 MPa.
Exam~le 21 Soda-lime flat-glass specimens were indented with a Vickers diamond to produce approximately 50-um flaws. These samples were tested with a concentric-ring fixture, and had average strengths of 69 MPa.
Flat-glass specimens were dip-coated with undiluted MPTMO, then cured by passing them three times through a W
curing apparatus at an energy level of S.3 Joule~ per square centimeter per pa~. The mean strength of specimens so treated was increased to 104 MPa.
ExamPle 22 Soda-lime flat-glass specimens were indented as set forth in Example 21, and then coated with 150~ of pyrolyti-cally deposited SnO2. The samples were then annealed to remove residual stresses. Tin-oxide-coated control samples had strengths of about 83 MPa.

~wo 95,00259 2 1 4 2 9` 0 4 PCT~S94/07~34 The SnO2-coated specimens were then treated with a 10 wt.% solution of MTMO as described in Examples 3 and 4, producing specimens with strengths of 210 MPa.
ExamPle 23 Soda-lime flat-glass specimens were indented with a Vickers diamond to produce approximately 50-um flaws. These samples were tested with a concentric-ring fixture, and had average strengths of 69 MPa. A solution of 10 wt.% of 3,3-dimethoxypropyltrimethoxysilane (DMPTMO) in water was prepared, and the pH ad~usted to 3.5. After st~n~ing for two hours at room temper~ture, one portion of the solution was used to drip-coat the flawed slides. The slides were then cured at 125C for 15 min. and then at 225C for 10 min. The mean strength for the treated slide~ was 88 MPa. lH nuclear-magnetic-resonance (NMR) analysis of the DMPTMO solution showed only the -CH(OCH3)2 group of the silane triol as a signal at 4.41 (triplet) ppm.
Another portion of the same solution, after st~n~ing 192 hours at room temperature, was used to drip-coat different slides flawed $dentically, and then cured as above. The mean strength of these slide~ was 256 MPa. NMR analysis of this solution showed -CH(OH)(CH3), -CH(OH)2, and -CHO group~ of 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, respectively.

wog5/~259 ~ &~ PCT~S91,~7~34 ExamPle 24 The present invention was tested at a bottling manufacturing facility based on the following procedure: 120 16-ounce glass beverage containers were pressure tested prior to treatment using an AGR ramp pressure tester. The average burst pressure measured was 422 psi (2.9 MPa), and the percentage of the bottles failing below 300 psi (2.1 MPa) was 15%. The treatment process consisted of spraying a solution of the present invention (specifically, CETMO), thermally curing to achieve 230C or better, followed by a st~n~rd cold-end-coating application. 120 containers having this treatment were burst-pressure tested in the same manner as those described above, yielding an average burst pressure of 490 psi (3.4 MPa) (increase of 16%) and a failure rate below 300 psi (2.1 MPa) of 6% (a decreass of 57%).
ExamPle 25 Vickers indented float glass was drip coated with an aqueous 10% solution of 3-ureidopropyltrimethoxysilane (UPTMO) having a pH of 3.4 and 0.05~ ~riton X-102 surfactant.
The samples were thereafter heat treated at 125C for 15 minutes followed by 225C for 10 minutes. The concentric ring strengths were uncoated 9588 psi (66.1 MPa) coated 25492 psi (176 MPa) ExamPle 26 Example 25 was repeated with the exception that the silane was 1,2-bis(trimethoxysilyl)ethane. The control samples had an average concentric ring strength of 11566 psi ~ 09s/~C59 2 I 4 2 9 0 4 PCT~S94/07~4 (79.8 MPa). After coating and curing, the average concentricring strength was 19728 psi (136 MPa).
ExamPle 27 Example 26 was again repeated with the exception that the heat treatment consisted of only heating at 125C for 15 minutes. The average strength went from 11566 psi (79.8 MPa) (uncoated) to 23799 psi (164 MPa) after co~ting and curing.
ExamPle 28 Example 25 was repeated with the exception that the silane was 1,2-bis(3-trimethoxysilylpropoxy)ethane. BTMOPE
was made using the following procedure.
Allyl bromide, 0.7 mole, was added dropwise over 1.5 hrs. to a stirred mixture of 0.33 mole of ethylene glycol, 1.25 moles of 50 % aqueous sodium hydroxide and 0.025 mole of tributylmethylammonium chloride. The mixture was heated at 80 - 90 for 12 hours. The mixture was cooled to 25C and the aqueous phase separated and was discarded. 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 isolated by distillation under reduced pressure, b.p 89-90C @ 50 torr.
A mixture of 0.075 mole of BAOE and 50 microliters of platinum divinyl complex in xylene (Hul~ America, cat #
PC072) was heated to 85C. Trimethoxy~ilane, .160 mole, (Aldrich Chem. Co.) was added dropwise to the stirred mixture over a 2 hour period under an inert atmosphere. The mixture was stirred at 85C for 2 hours then distilled under reduced WOg5/~259 ~l 4~ PCT~S94/07034 pressure. BTMOPE was isolated as the fraction with a boiling point 135-136C at 0.25 torr. The concentric ring strengths of the samples changed from 10139 psi (69.9 MPa) (uncoated) to 29183 psi (201 MPa) after coating and curing.
ExamPle 29 Example 27 was repeated using the silane of Example 28.
The strength of the coated and cured samples averaged 30153 psi (208.0 MPa) while the controls average 10139 psi (6g.9 MPa).
ExamPle 30 0.5 wt.% Celestine Blue dye (CAS # 1562-90-9) was added to a 5~ solution of CETMO that also contained 0.025% Triton X-102 surfactant. The solution was then spray applied onto 16-oz beverage containers using 2.0 g of solution/bottle.
The samples were then heat treated for 33 seconds in an infrared oven set at 700C. The coated bottles had a uniform blue coating.
ExamPle 31 To a 10% CETMO solution contAi~ing 0.05% Triton X-102 surfactant was added 1 wt.% each of U~inul MS-40 (obtained from BASF Corp.) and Tinopal CBS-X (obtained from Ciba-Geigy Corp.). The ~olution was spray applied onto flat glass. The sample~ were heat treated using the method of Example 25.
The final coating thickness was 0.9 micrometers. The samples were measured for their W transmission before and after coating and curing. The~results showed:

wo 95/00259 2 ~ 4 2 9 0 4 PCT/USg4/07034 NOT TAKEN INTO CONSIDERATION
FOR THE PURPOSES
OF ~ r.KNATIONAL PRO~ ING

-WO9S/00259 PCT~S94/07034 ~ 4~ ~ 4 ~
MTEO and 0. gram of Triton X-102, applied in the same manner on the same type of bottles, exhibited no retention of the label (adhesive failure).
Example 33 Rectangular alumlna bars were tested in 3-point bending to evaluate the ability of the present invention to strengthen it. Half of the alumina samples (n = 6) were tested as controls using the Instron configured in a 3-point bend arrangement. The other half of the samples were spray-coated with 10% by weight CETMO/0.02~% by weight Triton X-102/0.025 % by weight RP-40 (obtained from T.H.
Goldschmidt, Germany) formulation and thermally cured using the 2-step heat treatment protocol (15 minutes at 125C
followed by 10 minutes at 225C). The control samples had an average failure strenqth of 23,300 psi, while the treated samples had an average strength of 28,200 psi. This represents an average increase of 21%.
In view of the results reported by Hashimoto et al. in U.S. Patent No. 4,891,241, with respect to their comparative examples 1, 2 and 3, given at col. 25, lines 27 through 2g, where they found no increase in strength when only silanes were used as a coating, the de~ree of imp-o~e...-nt in strength afforded by the treatment of the examples describing the present invention is quite surprising. As noted in the present specification, no additional treatment, such as described by Hashimoto et al., is used, yet the improvement in strength of the treated glass rises to two or more times W095/00259 ~1 ~2 0= _ PCT~S94/07034 Y~
that of the untreated controls, and the variability in observed strengthening is relatively small. The improvement afforded by the present invention is especially surprising in view of the teaching of Hashimoto et al. at col. 5, lines 36 - et seq., where they note that the treatment of the substrate with siloxanes alone is insufficient to produce strengthening, and that a polymeric overcoat is essential for the development o the strengths reported.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specifica-tion and practice of the invention disclosed herein. It is intended that the specification and example~ to be considered as exemplary only, with a true scope and spirit of the inven-tion being indicated by the following claims.

Claims (48)

1. A method of strengthening a brittle oxide substrate comprising the steps of:
a) coating the brittle oxide substrate with an aqueous solution containing a silane-based composition in the substantial absence of an organic solvent, wherein the silane-based composition upon being hydrolyzed in the aqueous solution has the formula:

(OH)3SiR"
with R" being an organofunctional group; and b) curing the coating to form a transparent layer on the brittle oxide substrate;
wherein R" in the silane-based composition is selected so that (i) the strength of the brittle oxide substrate having the cured coating is substantially improved compared to the strength of the brittle oxide strength prior to the coating step and (ii) the cured coating does not interfere with the labelability of the brittle oxide substrate.

2. The method of claim 1, wherein R" is selected from the group consisting of glycidoxypropyl, 2-(3,4 epoxycyclo-hexyl)ethyl, 3,3-dimethoxypropyl, 3-ureidopropyl, hydrolyzed forms thereof and mixtures thereof.

3. The method of claim 1, wherein said organofunctional group is a residue of a hydrolyzable silane.

4. The method of claim 1, wherein the labelability of the brittle oxide substrate is greater than about 50% as measured by label peel test.

5. The method of claim 1, wherein the labelability of the brittle oxide substrate is greater than about 60% as measured by label peel test.

6. The method of claim 1, wherein the brittle oxide is glass.

7. The method of claim 1, wherein the silane-based composition chemically reacts with the brittle oxide substrate upon curing.

8. The method of claim 1, wherein the silane-based composition further contains at least one of the following:
a lubricant, a dye, a fluorescing agent, and/or UV blocker.

9. The method of claim 1, further comprising the step of applying a metal oxide layer to the brittle oxide substrate prior to step (a).

10. A method of strengthening a brittle oxide substrate comprising the steps of:
a) coating the brittle oxide substrate with an aqueous solution containing a silane-based composition in the substantial absence of an organic solvent, wherein the silane-based composition upon being hydrolyzed in the aqueous solution has the formula:

(OH)3SiR"
and b) curing the coating to form a transparent layer on the brittle oxide substrate;
wherein R" in the silane-based composition is selected so that (i) the strength of the brittle oxide substrate having the cured coating is substantially improved compared to the strength of the brittle oxide strength prior to the coating step and (ii) the substantially improved strength from the cured coating on the brittle oxide substrate has a maintained humidity resistance of at least about 50%.

11. The method of claim 10, wherein R" is vinyl or methyl.

12. The method of claim 10, wherein the brittle oxide is glass.

13. The method of claim 10, wherein the silane-based composition chemically reacts with the brittle oxide substrate upon curing.

14. The method of claim 10, wherein the silane-based composition further contains at least one of the following:
a lubricant, a dye, a fluorescing agent, and/or UV blocker.

15. The method of claim 10, further comprising the step of applying a metal oxide layer to the brittle oxide substrate prior to step (a).

16. The method of claim 10, wherein said organofunctional group is a residue of a hydrolyzable silane.

17. A method of strengthening a glass container comprising the steps of:
a) coating a surface of the glass container with an aqueous solution containing a silane-based composition in the substantial absence of an organic solvent, wherein the silane composition upon being hydrolyzed in the aqueous solution has the formula:

(OH)3SiR"

with R" being an organofunctional group ; and b) curing the coating to form a transparent layer on the surface of the glass container;

wherein the R" in the silane-based composition is selected so that (i) the strength of the glass container having the cured coating is substantially improved compared to the strength of the glass container prior to the coating step and (ii) the cured coating does not interfere with the labelability of the outer surface of the glass container.

18. The method of claim 17, wherein said organofunctional group is a residue of a hydrolyzable silane.

19. The method of claim 17, wherein R" is selected from the group consisting of glycidoxypropyl, 2-(3,4 epoxycyclo-hexyl)ethyl, 3,3-dimethoxypropyl, 3-ureidopropyl, hydrolyzed forms thereof and mixtures thereof.

20. The method of claim 17, wherein the labelability of the brittle oxide substrate is greater than about 50% as measured by label peel test.

21. The method of claim 17, wherein the labelability of the brittle oxide substrate is greater than about 60% as measured by label peel test.

22. The method of claim 17, wherein the pH of the silane-based composition is in the range of 1.5 to 11.

23. The method of claim 17, wherein the silane-based composition is in a concentration in the range of 1% to 99%
in the aqueous solution.

24. The method of claim 17, wherein the silane-based composition is a mixture of 2-(3,4 epoxycyclohexyl)ethyl trimethoxysilane, surfactant, and acidic water.

25. The method of claim 17, wherein the strength of the uncoated glass container is in the range of 10 to 600 psi as measured by burst pressure testing.

26. The method of claim 17, wherein the wall thickness of the glass container is in the range of 0.1 to 6 mm.

27. A silane coated brittle oxide container comprising:
(a) a brittle oxide container;
(b) a transparent layer of polymerized cross-linked siloxane cured onto a surface of the brittle oxide container, the polymerized cross-linked siloxane being formed from an aqueous silane-based composition substantially lacking an organic solvent and being selected from the group consisting of MPTMO, GPTMO, VTMO, CETMO, MTMO, DMPTMO, 3-ureidopropyltrimethoxysilane, 1,2-bis(trimethoxy-silyl)ethane, 1,2-bis(3-trimethoxysilylpropoxy)ethane, 5,6-epoxyhexyltrimethoxysilane, N-(trimethoxysilylpropyl)-maleic acid amide, hydrolyzed forms thereof and mixtures thereof.

28. The container of claim 27, wherein the container is a glass bottle.

29. The container of claim 28, wherein the glass bottle has a wall thickness in the range of 0.1 to 6 mm.

30. The container of claim 27, further comprising:
a label on the surface of the transparent layer of polymerized cross-linked siloxane.

31. The container of claim 30, wherein the labelability of the surface is greater than about 60% as measured by label peel test.

32. The container of claim 27, further comprising:
a layer of a metal oxide between the outer surface of the container and the transparent layer of polymerized cross-linked siloxane.

33. The container of claim 27, further comprising:
a lubricant coating on the surface of the layer of polymerized cross-linked siloxane.

34. The container of claim 33, further comprising:
a label on the surface of the lubricant coating.

35. The method of claim 1, wherein said silane-based composition is a mixture of MTMO and hydrolyzed CETMO, or a mixture of MTMO, hydrolyzed CETMO and hydrolyzed GPTMO, or a mixture of hydrolyzed CETMO and hydrolyzed GPTMO, or a mixture of VTMO and hydrolyzed CETMO or a mixture of hydrolyzed DMPTMO and hydrolyzed CETMO.

36. A method to restore strength to a brittle oxide substrate comprising the steps of:
a) coating the brittle oxide substrate with an aqueous solution containing a silane-based composition in the substantial absence of an organic solvent, wherein the silane-based composition upon being hydrolyzed in the aqueous solution has the formula:
(OH)3SiR"
with R" being an organofunctional group; and b) curing the coating to form a transparent layer on the brittle oxide substrate;
wherein R" in the silane-based composition is selected so that (i) the strength of the brittle oxide substrate having the cured coating is substantially restored compared to the strength of the brittle oxide strength prior to the coating step and (ii) the cured coating does not interfere with the labelability of the brittle oxide substrate.

37. A method to partially or completely heal flaws in a tension-bearing surface comprising the steps of:
a) coating the tension-bearing surface with an aqueous solution containing a silane-based composition in the substantial absence of an organic solvent, wherein the silane-based composition upon being hydrolyzed in the aqueous solution has the formula:
(OH)3SiR"
with R" being an organofunctional group; and b) curing the coating to form a transparent layer on the tension-bearing surface;
wherein R" in the silane-based composition is selected so that (i) the strength of the tension-bearing surface having the cured coating is substantially improved compared to the strength of the tension-bearing surface strength prior to the coating step and (ii) the cured coating does not interfere with the labelability of the tension-bearing surface.

38. The method of claim 37, wherein said tension-bearing surface is a brittle oxide substrate.

39. The method of claim 37, wherein said tension-bearing surface is a glass container.

40. A composition useful for coating brittle oxide substrates comprising a mixture of CETMO and VTMO.

41. A composition useful for coating brittle oxide substrates comprising a mixture of CETMO and MTMO.

42. A composition useful for coating brittle oxide substrates comprising a mixture of GPTMO, CETMO and MTMO.

43. A composition useful for coating brittle oxide substrates comprising a mixture of GPTMO and CETMO.

44. A composition useful for coating brittle oxide substrates comprising UPTMO.

45. A composition useful for coating brittle oxide sub-strates comprising 1,2-bis(trimethoxysilyl)ethane.

46. A composition useful for coating brittle oxide sub-strates comprising 1,2-bis(3-trimethoxysilylpropoxy)ethane.

47. A composition useful for coating brittle oxide substrates comprising a mixture of DMPTMO and CETMO.

48. The method of claim 1, wherein the silane-based composition is applied to the brittle oxide substrate at a temperature of from about 80°C to about 100°C in order to create a diffused appearance upon curing.