US20030032721A1

US20030032721A1 - Composition for providing an abrasion resistant coating on a substrate with a matched refractive index: 2

Info

Publication number: US20030032721A1
Application number: US10/114,569
Authority: US
Inventors: Karl Terry; Bryan Lembo
Original assignee: Individual
Current assignee: Individual
Priority date: 1999-04-23
Filing date: 2002-04-01
Publication date: 2003-02-13
Also published as: US6538092B1

Abstract

The present invention discloses compositions as well as methods of making and using said compositions, having improved stability which, when applied to a variety of substrates and cured, form transparent coatings having abrasion resistant properties and a matched refractive index to that of the substrate. The compositions comprise an aqueous-organic solvent mixture containing a mixture of hydrolysis products and partial condensates of an epoxy-functional silane, a carboxylic acid functional compound selected from the group consisting of carboxylic acids, multifunctional carboxylic acids, anhydrides, and combinations thereof, a metal oxide composite colloid, a colloidal silica material, and a tetrafunctional silane. The coating compositions of the present invention may further include a mixture of hydrolysis products and partial condensates of one or more silane additives.

Description

CROSS REFERENCE TO RELATED APPLICATIONS

This is an application from U.S. Provisional Serial No. 60/130,768, filed Apr. 23, 1999, entitled COMPOSITION FOR PROVIDING AN ABRASION RESISTANT COATING ON A SUBSTRATE WITH A MATCHED REFRACTIVE INDEX:2.[0001]

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not Applicable.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to coating compositions and methods of making and using same, and more particularly but not by way of limitation, to coating compositions which, when cured, provide substantially transparent coatings having abrasion resistance and a matched refractive index to that of the substrate.

The present invention also relates to liquid coating compositions and methods of making and using same having improved abrasion resistance and improved stability wherein the liquid coating compositions are derived from aqueous-organic solvent mixtures containing effective amounts of an epoxy-functional silane, colloidal metal oxide composite, a tetrafunctional silane, and colloidal silica.

2. Description of Prior Art

Silica based coatings deposited on plastic materials are useful for their abrasion resistance and weatherability and thus extend the useable life of the plastic material. These coatings, in most cases, do not match the refractive index of the plastic material and allow for interference patterns to arise due to the refractive index mismatch between the cured coating film and the plastic substrate material. This mismatch leads to increased reflectivity of the coated plastic material and to exacerbation of material flaws due to the increased reflectivity.

BRIEF SUMMARY OF THE INVENTION

The present invention provides compositions having improved stability which, when applied to a variety of substrates and cured, form transparent coatings having abrasion resistant properties and a matched refractive index to that of the substrate as well as methods of making and using said coating compositions.

Broadly, the coating compositions of the present invention comprise an aqueous-organic solvent mixture containing from about 10 to about 90 weight percent, based on the total solids of the composition, of a mixture of hydrolysis products and partial condensates of an epoxy-functional silane, from about 1 to about 90 weight percent, based on the total weight of the composition, of a carboxylic acid functional compound selected from the group consisting of carboxylic acids, multifunctional carboxylic acids, anhydrides, and combinations thereof, from about 1 to 90 weight percent, based on the total solids of the composition, of a metal oxide composite colloid, from about 1 to 75 weight percent, based on the total solids of the composition, of a colloidal silica material, and from about 1 to 75 weight percent, based on the total solids of the composition, of a tetrafunctional silane.

The coating compositions of the present invention may further include from about 0.1 to about 50 weight percent of a mixture of hydrolysis products and partial condensates of one or more silane additives, based on the total solids of the composition.

It is an object of the present invention to provide coating compositions having improved stability, which form transparent coatings upon curing. It is a further object of the present invention to provide stable coating compositions, which form transparent coatings upon curing which have improved adhesion properties, improved resistance to crack formation, and a matched refractive index to that of the substrate.

Other objects, advantages and features of the present invention will become apparent upon reading the following detailed description in conjunction with the appended claims.

DETAILED DESCRIPTION OF THE INVENTION

Before explaining at least one embodiment of the invention in detail, it is to be understood that the invention is not limited in its application to the details of construction and the arrangement of the components set forth in the following description. The invention is capable of other embodiments or of being practiced or carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein is for the purpose of description and should not be regarded as limiting.

The present invention relates to coating compositions having improved stability which, when applied to a variety of substrates and cured, form substantially transparent abrasion resistant coatings which possess improved adhesion, improved resistance to crack formation, and have a matched refractive index to that of the substrate.

For measuring the refractive indexes of the cured coating compositions, each composition was applied to a cleanly etched lead-silicate glass plaque by dip coating at 2 inches per minute and curing for a period of 1 hour at 120° C. The refractive indexes were measured using a Bausch and Lomb Abbe-3L refractometer. Either diiodomethane or 1-bromonaphthalene was used as the contact liquid. The standard procedures for measurement and instrument maintenance contained in the operator's manual for the Bausch and Lomb Abbe-3L refractometer were used for data gathering and processing. For testing coated samples, coating compositions were applied to ADC lenses and cured at a temperature in the range from 95° C. to 120° C. for a period of 3 hours. Semi-quantitative assessments of the extent of cracking and adhesion were made using the following tests.

For testing adhesion of the coated articles the procedures of ASTM D-3359, i.e. the tape test, were followed.

A typical test for cracking and adhesion consists of immersion of the coated article in boiling water or boiling tap water tint for a period of time, e.g. 30 minutes, followed by inspection for crack formation and testing for adhesion. Specifically, lenses were tested in BPI Black Tint (Brain Power, Inc.) under boiling conditions. In this test a bottle of BPI tint (approximately 100 grams) was diluted to about 900 grams with tap water and brought to a boil. The coated article was immersed in the boiling solution for a period of 30 minutes. The coated article was removed from the tint solution and inspected for cracking and tested for adhesion.

For testing abrasion resistance of coated substrates, any of a number of quantitative test methods maybe employed, including the Taber Test (ASTM D-4060), the Tumble Test and Standard Method for the Modified Bayer Test, which is described in The AR Council of America Standard Testing Procedures section 5.2.5 and is a variation of the test method, ASTM F735-81. In addition, there are a number of qualitative test methods that may be used for measuring abrasion resistance, including the Steel Wool Test and the Eraser Test. In the Steel Wool Test and the Eraser Test, sample coated substrates are scratched under reproducible conditions (constant load, frequency, etc.). The scratched test samples are then compared and rated against standard samples. A semi-quantitative application of these test methods involves the use of an instrument, such as a Spectrophotometer or a Colorimeter, for measuring the scratches on the coated substrate as a haze gain.

The measured abrasion resistance of a cured coating on a substrate, whether measured by the Modified Bayer Test, Taber Test, Steel Wool Test, Eraser Test, Tumble Test, etc. is a function, in part, of the cure temperature and cure time. In general, higher temperatures and longer cure times result in higher measured abrasion resistance. Normally, the cure temperature and cure time are selected for compatibility with the substrate; although, sometimes less than optimum cure temperatures and cure times are used due to process and/or equipment limitations. It will be recognized by those skilled in the art that other variables, such as coating thickness and the nature of the substrate, will also have an effect on the measured abrasion resistance. In general, for each type of substrate and for each coating composition there will be an optimum coating thickness. The optimum cure temperature, cure time, coating thickness, and the like, can be readily determined empirically by those skilled in the art.

In the test method employed to determine the abrasion resistance of the coating compositions of the present invention, a commercially available alundum (grain code 1524, 12 grit, alundum ZF) sold by Norton Advanced Ceramics of Canada Inc., 8001 Daly Street, Niagara Falls, Ontario, was used as the abrasive material. In this test, 540 grams alundum was loaded into a 9{fraction (5/16)}″×6¾″ cradle fitted with four lenses. Each set of four lenses, typically two poly(diethylene glycol-bis-allyl carbonate) lenses, herein referred to as ADC lenses, and two coated lenses, were subjected to a 4 inch stroke (the direction of the stroke coinciding with the 9{fraction (5/16)}″ length of the cradle) at an oscillation frequency of 300 strokes per minute for a total of 4 minutes. The lens cradle was repositioned by turning 180 degrees after the initial 2 minutes of oscillations. Repositioning of the cradle was used to reduce the impact of any inconsistencies in the oscillating mechanism. The ADC reference lenses used were Silor 70 mm plano FSV lenses, purchased through Essilor of America, Inc. of St. Petersburg, Fla. The above described procedure is slightly modified from that which is described by the AR Council of America by increasing the weight of the alundum to accommodate the increased surface area of the larger cradle. The cradle described above holds 4 lenses.

The haze generated on the lenses was then measured on a Gardner XL-835 Colorimeter. The haze gain for each lens was determined as the difference between the initial haze on the lenses and the haze after testing. The ratio of the haze gain on the ADC reference lenses to the haze gain on the coated sample lenses was then reported as the resultant abrasion resistance of the coating material. A ratio of greater than 1 indicates a coating which provides greater abrasion resistance than the uncoated ADC reference lenses. This ratio is commonly referred to as the Bayer ratio, number or value. Coatings with high abrasion resistance possess larger Bayer numbers than coatings with lower abrasion resistance.

It should be understood that: (a) the descriptions herein of coating systems which contain epoxy-functional silanes, tetrafunctional silanes, silane additives which do not contain an epoxy-functional group, and the carboxylic acid component, refer to the incipient silanes and carboxylic acid components from which the coating system is formed, (b) when the epoxy-functional silanes, tetrafunctional silanes, and silane additives which do not contain an epoxy-functional group, are combined with the aqueous-organic solvent mixture under the appropriate conditions, a hydrolysis reaction occurs resulting in partially or fully hydrolyzed species, (c) the resultant fully or partially hydrolyzed species can combine to form mixtures of multifunctional oligomeric siloxane species, (d) the oligomeric siloxane species may or may not contain pendant hydroxy and pendant alkoxy moieties and will be comprised of a silicon-oxygen matrix which contains both silicon-oxygen siloxane linkages and silicon-oxygen carboxylic acid component linkages, (e) the resultant mixtures are dynamic oligomeric suspensions that undergo structural changes which are dependent upon a multitude of factors including; temperature, pH, water content, catalyst concentration, and the like.

The coating compositions of the present invention comprise an aqueous-organic solvent mixture containing from about 10 to about 90 weight percent, based on the total solids of the composition, of a mixture of hydrolysis products and partial condensates of an epoxy-functional silane, from about 1 to about 90 weight percent, based on the total weight of the composition, of a carboxylic acid functional compound selected from the group consisting of carboxylic acids, multifunctional carboxylic acids, anhydrides, and combinations thereof, from about 1 to 90 weight percent, based on the total solids of the composition, of a metal oxide composite colloid, from about 1 to 75 weight percent, based on the total solids of the composition, of a colloidal silica material, and from about 1 to 75 weight percent, based on the total solids of the composition, of a tetrafunctional silane.

The amount of epoxy-functional silane, carboxylic acid component, metal oxide composite sol, colloidal silica, and tetrafunctional silane employed can vary widely and will generally be dependent upon the properties desired in the coating composition and the cured coating, as well as the end use of the substrate to which the coating composition is applied. Generally, however, desirable results can be obtained where the molar ratio of the epoxy-functional silane component to the colloidal silica component, tetrafunctional silane component, and the colloidal metal oxide component are present in the coating composition at a ratio of from about 0.05:1 to 2:1, the molar ratio of the colloidal silica component to the metal oxide composite colloid present in the coating composition is present in a range of from about 0.01:1 to about 50:1, and the molar ratio of the tetrafunctional silane component to the metal oxide composite colloid present in the coating composition is present in a range of from about 0.01 to 1 to about 50:1.

While the presence of water in the aqueous-organic solvent mixture is necessary to form hydrolysis products of the silane components of the mixture, the actual amount of water can vary widely. However, a sufficient amount of water must be present in the aqueous-organic solvent mixture to provide a substantially homogeneous coating mixture of hydrolysis products and partial condensates of the alkoxy functional silanes (i.e., the epoxy-functional silane and other silane additive components) which, when applied and cured on an article, provides a substantially transparent coating. Such coatings can be obtained by employing a stoichiometric amount of water, e.g., as required for the hydrolysis of the sum of the hydrolyzable alkoxy groups on the alkoxy silane components in the coating mixture. The abrasion resistance of the coated article is affected by the concentration of water in the incipient coating mixture, as well as the presence and concentration of a condensation catalyst.

For example, coating mixtures which contain a low concentration of water (e.g. a stoichiometric concentration of water) require a optional mineral acid hydrolysis co-catalyst to ensure sufficient hydrolysis necessary for the formation of a homogeneous coating mixture and a condensation catalyst to obtain coating compositions which possess the desired abrasion resistance properties after curing. It is preferred that the amount of water present in the aqueous-organic solvent mixture will range from about 1 to about 10 equivalents of water for each hydrolyzable alkoxy group. The effective amount of water and the effective amount and type of catalyst can be determined empirically.

The solvent constituent of the aqueous-organic solvent mixture of the coating compositions of the present invention can be any solvent or combination of solvents which is compatible with the epoxy-functional silane, the carboxylic acid component, the colloidal metal oxide component, the colloidal silica component, and the tetrafunctional silane component. For example, the solvent constituent of the aqueous-organic solvent mixture may be an alcohol, an ether, a glycol or a glycol ether, a ketone, an ester, a glycolether acetate and mixtures thereof. Alcohols which can be employed as the solvent constituent are represented by the formula ROH where R is an alkyl group containing from 1 to about 10 carbon atoms. Examples of alcohols which can be employed as the solvent constituent of the aqueous-organic solvent mixture employed in the practice of the present invention are methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, cyclohexanol, pentanol, octanol, decanol, and mixtures thereof

Glycols, ethers, and glycol ethers which can be employed as the solvent constituent of the aqueous-organic solvent mixture are represented by the formula R ¹—(OR²)_x—OR¹where x is 0, 1, 2, 3 or 4, R¹is hydrogen or an alkyl group containing from 1 to about 10 carbon atoms and R²is an alkylene group containing from 1 to about 10 carbon atoms and combinations thereof.

Examples of glycols, ethers and glycol ethers having the above-defined formula and which may be used as the solvent constituent of the aqueous-organic solvent mixture of the coating compositions of the present invention are di-n-butylether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol dibutyl ether, ethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, ethylene glycol ethyl ether, ethylene glycol diethyl ether, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, dibutylene glycol, tributylene glycol and mixtures thereof. In addition to the above, cyclic ethers such as tetrahydrofuran and dioxane are suitable ethers for the aqueous-organic solvent mixture.

Examples of ketones suitable as the organic solvent constituent of the aqueous-organic solvent mixture are acetone, diacetone alcohol, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone and mixtures thereof.

Examples of esters suitable as the organic solvent constitutent of the aqueous-organic solvent mixture are ethyl acetate, n-propyl acetate, n-butyl acetate and combinations thereof.

Examples of glycolether acetates suitable as the organic solvent constituent of the aqueous-organic solvent mixture are propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, ethyl 3-ethoxypropionate, ethylene glycol ethyl ether acetate and combinations thereof.

The epoxy-functional silane useful in the formulation of the coating compositions of the present invention can be any epoxy-functional silane which is compatible with the carboxylic acid component, the metal oxide composite colloid, the colloidal silica components, and the tetrafunctional silane component of the coating composition, and which provides a coating composition which, upon curing, produces a substantially transparent, abrasion resistant coating which exhibits improved adhesion and improved resistance to crack formation and which possesses a refractive index substantially corresponding to the refractive index of the substrate on which the coating composition is applied. Generally, such epoxy-functional silanes are represented by the formula R ³ _xSi(OR⁴)_4-xwhere x is an integer of 1, 2 or 3, R³is H, an alkyl group, a functionalized alkyl group, an alkylene group, an aryl group, an alkyl ether, and combinations thereof containing from 1 to about 10 carbon atoms and having at least 1 epoxy-functional group, and R⁴is H, an alkyl group containing from 1 to about 5 carbon atoms, an acetyl group, a —Si(OR⁵)_3-yR⁶ _ygroup where y is an integer of 0, 1, 2, or 3, and combinations thereof where R⁵is H, an alkyl group containing from 1 to about 5 carbon atoms, an acetyl group, or another —Si(OR⁵)_3-yR⁶ _ygroup and combinations thereof, and R⁶is H, an alkyl group, a functionalized alkyl group, an alkylene group, an aryl group, an alkyl ether, and combinations thereof containing from 1 to about 10 carbon atoms which may also contain an epoxy-functional group.

Examples of such epoxy-functional silanes are glycidoxy methyltrimethoxysilane, 3-glycidoxypropyltrihydroxysilane, 3-glycidoxypropyldimethylhydroxysilane, 3-glycidoxypropyltrimeth-oxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyl-dimethoxymethylsilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyltributoxysilane, 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, 1,3-bis(glycidoxypropyl)tetramethoxydisiloxane, 1,3-bis(glycidoxypropyl)-1,3-dimethyl- 1,3-dimethoxydisiloxane, 2,3-epoxypropyltrimethoxysilane, 3,4-epoxybutyltrimethoxysilane, 6,7-epoxyheptyltrimethoxysilane, 9,10-epoxydecyltrimethoxysilane, 1,3-bis(2,3-epoxypropyl)tetramethoxydisiloxane, 1,3-bis(6,7-epoxyheptyl)tetramethoxydisiloxane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like.

The coating compositions of the present invention contain any carboxylic acid component compatible with the epoxy-functional silane, the colloidal metal oxide component, the colloidal silica component, and the tetrafunctional silane. The carboxylic acid component is capable of interacting with the hydrolysis products and partial condensates of the epoxy-functional silane and the tetrafunctional silane to provide a coating composition which, upon curing, produces a substantially transparent, abrasion resistant coating having improved adhesion and improved crack resistance and which possesses a refractive index substantially corresponding to the refractive index of the substrate on which the coating composition is applied.

Carboxylic acid component as used herein is understood to include mono- and multifunctional carboxylic acids as well as anhydrides, which produce mono- and multifunctional carboxylic acids. Examples of carboxylic acids which can be in the coating compositions of the present invention include acetic acid, acrylic acid, methacrylic acid, formic acid, propionic acid, butanoic acid, benzoic acid, malic acid, aconitic acid (cis,trans), itaconic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, cyclohexyl succinic acid, 1,3,5 benzene tricarboxylic acid, 1,2,4,5 benzene tetracarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,1-cyclohexanediacetic acid, 1,3-cyclohexanediacetic acid, 1,3,5-cyclohexanetricarboxylic acid and unsaturated dibasic acids such as fumaric acid and maleic acid and combinations thereof.

Examples of anhydrides which can be employed to produce the carboxylic acid component of the coating compositions of the present invention include the anhydrides of the above mentioned carboxylic acids such as acetic anhydride, propionic anhydride, acrylic anhydride, methacrylic anhydride and the cyclic anhydrides of the above mentioned dibasic acids such as succinic anhydride, itaconic anhydride, glutaric anhydride, trimellitic anhydride, pyromellitic anhydride, phthalic anhydride and maleic anhydride and combinations thereof.

Optionally, in addition to the carboxylic acid component of the coating composition, a mineral acid such as, for example, hydrochloric acid or nitric acid, can be used as a co-hydrolysis catalyst for the hydrolysis of the silane compounds described herein.

The metal oxide colloidal component of the present invention may consist of a single component metal oxide colloid or a complex composite metal oxide colloid consisting of more than one metal oxide component. The refractive index of the colloidal metal oxide component should be sufficiently higher than the coating mixture so the addition of effective amounts of the colloidal metal oxide component can yield a desirable refractive index for the entire coating composition. The colloidal metal oxide component may contain any combination of titania, zirconia, tin oxide, antimony oxide, iron oxide, lead oxide, and/or bismuth oxide for purposes of increasing the refractive index. The colloidal metal oxide component may also contain alumina and/or silica. In general, it is preferred that the colloidal metal oxide component used in the present invention consist of a composite mixture of two or more metal oxide components listed above where at least one of the metal oxide components present in the composite mixture is neither alumina nor silica.

Examples of commercially available metal oxide colloidal materials and composite metal oxide component materials are the Suncolloid series AMT-130S, HIS-33M, HIT-30M, and HIT-32M from Nissan Chemical Industries LTD., Optolake 1130F-2(A-8), 2130F-2(A-8), Optolake ARC-7 and Optolake PH-1, and Queen Titanic-11-1 from Catalyst and Chemical Industries LTD. Proper selection of the amounts and type of the colloidal metal oxide component, the epoxy-functional silane, the carboxylic acid component, the colloidal silica component, the tetrafunctional silane component, and optionally if desired, the optional silane component and condensation catalyst will yield a cured coating material with a refractive index in the range from 1.4 to greater than 1.7 refractive index units.

The colloidal silica component of the present invention can be either an aqueous or non-aqueous based material. The colloidal silica is an aqueous or non-aqueous solvent dispersion of particulate silica and the various products differ principally by particle size, silica concentration, pH, presence of stabilizing ions, solvent makeup, and the like. Colloidal silica is commercially available under a number of different tradename designations, including Nalcoag® (Nalco Chemical Co., Naperville, Ill.); Nyacol® (Nyacol Products, Inc., Ashland, Mass.); Snowtex® (Nissan Chemical Industries, LTD., Tokyo, Japan); Ludox® (DuPont Company, Wilmington, Del.); and Highlink OG® (Hoechst Celanese, Charlotte, N.C.). It should be noted that substantially different product properties can be obtained through the selection of different colloidal silicas.

Colloids which possess acidic pH values and very slightly basic pH values with low levels of sodium are preferred. These colloidal silica materials provide an increase in the abrasion resistance and provide a resistance to crack formation, which can result from exposure of the cured coatings to boiling tap water tint baths, vide supra. Examples of preferred colloidal silica materials are Nalco® 1042 and Nalco® 1040 and the like. Basic colloidal silica materials which possess higher pH values and/or a higher concentration of sodium ions result in cured coating compositions which possess abrasion resistance which is lower than that which results from the use of the preferred colloidal silica materials and are not preferred. An example of a material, which is not preferred is Nalco® 1115 and the like.

The tetrafunctional silanes useful in the formulation of the coating compositions of the present invention are represented by the formula Si(OR ⁷)₄where R⁷is H, an alkyl group containing from 1 to about 5 carbon atoms and ethers thereof, an (OR⁷) carboxylate, a —Si(OR⁸)₃group where R⁸is a H, an alkyl group containing from 1 to about 5 carbon atoms and ethers thereof, an (OR⁷) carboxylate, or another —Si(OR⁸)₃group and combinations thereof. Examples of tetrafunctional silanes represented by the formula Si(OR⁷)₄are tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, tetraisopropyl orthosilicate, tetrabutyl ortho-silicate, tetraisobutyl orthosilicate, tetrakis(methoxyethoxy) silane, tetrakis(methoxypropoxy)silane, tetrakis(ethoxyethoxy) silane, tetrakis(methoxyethoxyethoxy)silane, trimethoxyethoxy-silane, dimethoxydiethoxysilane, triethoxymethoxysilane, poly- (dimethoxysiloxane), poly(diethoxysiloxane), poly(dimethoxy-diethoxysiloxane), tetrakis(trimethoxysiloxy)silane, tetrakis-(triethoxysiloxy)silane, and the like. In addition to the R⁷and R⁸substituants described above for the tetrafunctional silane, R⁷and R⁸taken with oxygen (OR⁷) and (OR⁸) can be carboxylate groups. Examples of tetrafunctional silanes with carboxylate function-alities are silicon tetracetate, silicon tetrapropionate and silicon tetrabutyrate.

The coating compositions of the present invention are also stable with respect to aging, both in terms of performance and solution stability. The aging of the coating compositions is characterized by a gradual increase in viscosity, which eventually renders the coating compositions unusable due to processing constraints. The coating compositions of the present invention, when stored at temperatures of 5° C. or lower have usable shelf lives of 3-4 months. During this period, the abrasion resistance of the cured coatings does not significantly decrease with time. The abrasion resistant coating compositions which provide index matching properties described in the present invention are achieved through the unique combination of an epoxy-functional silane, a carboxylic acid component, a composite metal oxide colloid, a colloidal silica component, and a tetrafunctional silane. The coating compositions may optionally include other materials which may: (a) enhance the stability of the coating compositions; (b) increase the abrasion resistance of cured coatings produced by the coating compositions; (c) improve processing of the coating compositions; and (d) provide other desirable properties to the coating composition and the cured product of the coating compositions.

The coating compositions of the present invention may further include from about 0.1 to about 50 weight percent, based on the weight of total solids of the coating compositions, of a mixture of hydrolysis products and partial condensates of one or more silane additives (i.e, trifunctional silanes, difunctional silanes, monofunctional silanes, and mixtures thereof). The selection of the silane additives incorporated into the coating compositions of the present invention will depend upon the particular properties to be enhanced or imparted to either the coating composition or the cured coating composition. The silane additives are represented by the formula R ⁹ _xSi(OR¹⁰)_4-xwhere x is a 1, 2 or 3; R⁹is H, or an alkyl group containing from 1 to about 10 carbon atoms, a functionalized alkyl group, an alkylene group, an aryl group an alkyl ether group and combinations thereof; R¹⁰is H, an alkyl group containing from 1 to about 10 carbon atoms, an acetyl group, a —Si(OR¹⁰)₃group and combinations thereof.

Examples of silane additives represented by the above-defined formula are methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexylmethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, dimethyldimethoxysilane, 2-(3-cyclohexenyl)ethyltrimethoxysilane, 3-cyanopropyl-trimethoxysilane, 3-chloropropyltrimethoxysilane, 2-chloroethyltrimethoxysilane, phenethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, phenyltrimethoxysilane, 3-isocyanopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 4-(2-aminoethylaminomethyl)phenethyltrimethoxysilane, chloromethyltriethoxysilane, 2-chloroethyltriethoxysilane, 3-chloropropyltriethoxysilane, phenyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, cyclohexyl-triethoxysilane, cyclohexylmethyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltriethoxysilane, allyltriethoxysilane, [2-(3-cyclohexenyl)ethyltriethoxysilane, 3-cyanopropyltriethoxysilane, 3-methacrylamidopropyltriethoxysilane, 3-methoxypropyltrimethoxysilane, 3-ethoxypropyltrimethoxysilane, 3-propoxypropyltrimethoxysilane, 3-methoxyethyltrimethoxysilane, 3-ethoxyethyltrimethoxysilane, 3-propoxyethyltrimethoxysilane, 2-[methoxy(polyethyleneoxy)propyl]heptamethyltrisiloxane, [methoxy(polyethyleneoxy)propyl]trimethoxysilane, [methoxy(polyethylene-oxy)ethyl]trimethoxysilane, [methoxy(polyethyleneoxy)propyl]-triethoxysilane, [methoxy(polyethyleneoxy)ethyl]triethoxysilane, and the like.

Although a condensation catalyst is not an essential ingredient of the coating compositions of the present invention, the addition of a condensation catalyst can affect abrasion resistance and other properties of the coating including stability, tinting capacity, porosity, cosmetics, caustic resistance, water resistance and the like. When employing a condensation catalyst, the amount of catalyst used can vary widely, but will generally be present in an amount from about 0.05 to about 20 weight percent, based on the total solids of the composition.

Examples of catalysts which can be incorporated into the coating compositions of the present invention are (i) metal acetylacetonates, (ii) diamides, (iii) imidazoles, (iv) amines and ammonium salts, (v) organic sulfonic acids and their amine salts, (vi) alkali metal salts of carboxylic acids, (vii) alkali metal hydroxides, (viii) fluoride salts, and (ix) organostannanes. Thus, examples of such catalysts include for group (i) such compounds as aluminum, zinc, iron and cobalt acetylacetonates; group (ii) dicyandiamide; for group (iii) such compounds as 2-methylimidazole, 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-propylimidazole; for group (iv), such compounds as benzyldimethylamine, and 1,2-diaminocyclohexane; for group (v), such compounds as trifluoromethanesulfonic acid; for group (vi), such compounds as sodium acetate, for group (vii), such compounds as sodium hydroxide, and potassium hydroxide, for group (viii), tetra n-butyl ammonium fluoride, and for group (ix), dibutyltin dilaurate, and the like.

An effective amount of a leveling or flow control agent can be incorporated into the composition to more evenly spread or level the composition on the surface of the substrate and to provide substantially uniform contact with the substrate. The amount of the leveling or flow control agent can vary widely, but generally is an amount sufficient to provide the coating composition with from about 10 to about 50,000 ppm of the leveling or flow control agent. Any conventional, commercially available leveling or flow control agent which is compatible with the coating composition and the substrate and which is capable of leveling the coating composition on a substrate and which enhances wetting between the coating composition and the substrate can be employed. The use of leveling and flow control agents is well known in the art and has been described in the “Handbook of Coating Additives” (ed. Leonard J. Calbo, pub. Marcel Dekker), pg 119-145.

Examples of such leveling or flow control agents which can be incorporated into the coating compositions of the present invention include organic polyethers such as TRITON X-100, X-405, N-57 from Rohm and Haas, silicones such as Paint Additive 3, Paint Additive 29, Paint Additive 57 from Dow Corning, SILWET L-77, and SILWET L7600 from OSi Specialties, and fluorosurfactants such as FLUORAD FC-171, FLUORAD FC-430 and FLUORAD FC-431 from 3M Corporation.

In addition, other additives can be added to the coating compositions of the present invention in order to enhance the usefulness of the coating compositions or the coatings produced by curing the coating compositions. For example, ultraviolet absorbers, antioxidants, and the like can be incorporated into the coating compositions of the present invention, if desired.

The coating compositions of the present invention can be prepared by a variety of processes to provide stable coating compositions, which, upon curing, produce substantially transparent abrasion resistant coatings having improved abrasion resistance, resistance to crack formation, and a matched refractive index.

The preferred method for preparing the coating compositions of the present invention consists of the initial hydrolysis of the epoxy-functional silane by addition of the silane to a mixture of deionized water, the acid component, and the solvent constituent. After sufficient time for the hydrolysis, the tetrafunctional silane is added and the resultant mixture is allowed to stir for a sufficient period of time to allow for hydrolysis of the tetrafunctional silane. To this mixture colloidal silica is then added followed by slow addition of the metal oxide colloid to insure maximum homogeneity. When desired, a condensation catalyst and/or a surfactant for leveling and flow improvement may be added to the final coating composition.

The coating compositions of the present invention can be applied to solid substrates by conventional methods, such as flow coating, spray coating, curtain coating, dip coating, spin coating, roll coating, etc. to form a continuous surface film. Any substrate compatible with the compositions can be coated with the compositions, such as plastic materials, wood, paper, metal, printed surfaces, leather, glass, ceramics, glass ceramics, mineral based materials and textiles. The compositions are especially useful as coatings for synthetic organic polymeric substrates in sheet or film form, such as acrylic polymers, poly(ethyleneterephthalate), polycarbonates, polyamides, polyimides, copolymers of acrylonitrile-styrene, styrene-acrylonitrile-butadiene copolymers, polyvinyl chloride, butyrates, polyethylene and the like. Transparent polymeric materials coated with these compositions are useful as flat or curved enclosures, such as windows, liquid crystal display screens, skylights and windshields, especially for transportation equipment. Plastic lenses, such as acrylic or polycarbonate ophthalmic lenses, can also be coated with the compositions of the invention.

By choice of proper formulation, application conditions and pretreatment (including the use of primers) of the substrate, the coating compositions of the present invention can be adhered to substantially all solid surfaces. Abrasion resistant coatings having improved adhesion and resistance to cracking can be obtained from coating compositions of the present invention by heat curing at temperatures in the range of from about 50° C. to about 200° C. for a period of from about 5 minutes to about 18 hours. The coating thickness can be varied by means of the particular application technique, but coatings having a thickness of from about 0.5 to about 20 microns, and more desirably from about 1 to about 10 microns, are generally utilized.

In order to further illustrate the present invention, the following examples are given. However, it is to be understood that the examples are for illustrative purposes only and are not to be construed as limiting the scope of the subject invention.

EXAMPLES

Procedure [0057]
Etched poly(diethylene glycol-bis-allyl carbonate) lenses and plaques (referred to as ADC lenses or ADC plaques) were use for coating and testing. The ADC lenses and plaques were etched by contact with a 10% potassium hydroxide solution containing propylene glycol methyl ether and water for a period of about 10 minutes. The lenses and/or plaques were coated by dip coating using a specified withdrawal rate in units of inches per minute (ipm). The lenses and/or plaques were cured at a temperature of 110° C. for 3 hours. The lenses and/or plaques were subjected to the aforementioned test procedures to determine adhesion, resistance to cracking and abrasion resistance. [0058]

Example 1

63.0 grams of 3-glycidoxypropyltrimethoxy silane(GPTMS) were added dropwise to a solution composed of 92.8 grams of deionized water, 92.8 grams of propylene glycol methyl ether (PMOH), and 10.0 grams of acetic acid (AcOH). The aqueous-organic GPTMS mixture was stirred for 1 hour. To the mixture, 19.8 grams of TEOS were added dropwise and allowed to stir overnight. 16.8 grams of Nalco-1042 colloidal silica were added dropwise and the resulting mixture was stirred for approximately 4 hours. 104.7 grams of Optalake 2130f-2 (A-8), a colloidal metal oxide, were added dropwise and the resulting mixture was stirred overnight to yield a coating composition. [0059]
1.4 grams of a flow modifier comprising a PMOH-based solution containing 10 weight percent FC-430 (3M), were added to 190 grams of a coating composition prepared in accordance with the process described above. The coating composition was left to stir for an additional 10 to 30 minutes to insure mixing. This coating composition was applied to etched ADC lenses, ADC plaques and 1.7 R[0060] _Iplaques, according to the procedure above, at a withdrawal rate of 2 ipm to provide a cured coating having a thickness of about 1.9 microns, a refractive index of about 1.60, and a Bayer number of 8.9. After exposure to boiling tap water tint for 15 minutes, the coated lenses or plaques did not exhibit any crazing.

Example 2

63.0 grams of GPTMS were added dropwise to a solution composed of 95.5 grams of deionized water, 95.5 grams of PMOH, and 10.0 grams of AcOH. The aqueous-organic GPTMS mixture was stirred for 1 hour. To the mixture, 19.8 grams of TEOS were added dropwise and allowed to stir overnight. 11.4 grams of Nalco-1050 colloidal silica were added dropwise and the resulting mixture was stirred for approximately 4 hours. 104.7 grams of Optalake 2130f-2 (A-8), a colloidal metal oxide, were added dropwise and the resulting mixture was stirred overnight to yield a coating composition. [0061]
1.4 grams of a flow modifier comprising a PMOH-based solution containing 10 weight percent FC-430 (3M), were added to 190 grams of a coating composition prepared in accordance with the process described above. The coating composition was left to stir for an additional 10 to 30 minutes to insure mixing. This coating composition was applied to etched ADC lenses, ADC plaques and 1.7 R[0062] _Iplaques, according to procedure A, at a withdrawal rate of 2 ipm to provide a cured coating having a thickness of about 2.0 microns, a refractive index of about 1.60, and a Bayer number of 6.3. After exposure to boiling tap water tint for 15 minutes, the coated lenses or plaques did not exhibit any crazing.

Comparative Ex. A

63.0 grams of GPTMS were added dropwise to a solution composed of 91.3 grams of deionized water, 91.3 grams of PMOH, and 10.0 grams of AcOH. The aqueous-organic GPTMS mixture was stirred for 1 hour. To the mixture, 39.7 grams of TEOS were added dropwise and allowed to stir for 5 hours. 104.7 grams of Optalake 2130f-2 (A-8), a colloidal metal oxide, were added dropwise and the resulting mixture was stirred overnight to yield a coating composition. [0063]
1.4 grams of a flow modifier comprising a PMOH-based solution containing 10 weight percent FC-430 (3M), were added to 190 grams of a coating composition prepared in accordance with the process described in comparative example A. The coating composition was left to stir for an additional 10 to 30 minutes to insure mixing. This coating composition was applied to etched ADC lenses, ADC plaques and 1.7 R[0064] _Iplaques, according to the procedure above, at a withdrawal rate of 2 ipm to provide a cured coating having a thickness of about 1.9 microns, a refractive index of about 1.60, and a Bayer number of 10.0. After exposure to boiling tap water tint for 15 minutes, the coated lenses or plaques exhibited crazing.

Example 3a

26.7 grams of GPTMS were added dropwise to a stirring 49.5 grams of deionized water. The aqueous-organic GPTMS mixture was stirred for 1 hour. A solution of 4.6 grams of itaconic acid dissolved in 49.5 grams of PMOH were added quickly to the aqueous GPTMS mixture followed by 30 minutes of stirring. 8.4 grams of TEOS were added to the mixture and stirred overnight. To the resultant mixture, 7.1 grams of Nalco-1034A colloidal silica were added dropwise and allowed to stir for approximately 4 hours. 44.2 grams of Optalake 2130f-2 (A-8), a colloidal metal oxide, were added dropwise and the resulting mixture was stirred overnight to yield a coating composition. 0.14 grams of a surfactant solution, 10% PA-57 in PMOH, were added to the coating composition. To insure complete mixing, the coating mixture was stirred for an additional 10 to 30 minutes. This coating composition was applied to etched ADC lenses, ADC plaques and 1.7 R[0065] _Iplaques, according to the procedure above, at a withdrawal rate of 2 ipm to provide a cured coating having a thickness of about 2.2 microns, a refractive index of about 1.60, and a Bayer number of 5.5.

Example 3b

53.7 grams of GPTMS were added dropwise to a solution composed of 106.5 grams of deionized water, 29.4 grams of PMOH, and 9.2 grams of itaconic acid. The aqueous-organic GPTMS mixture was stirred for 1 hour. To the mixture, 16.9 grams of TEOS were added and stirred overnight. 14.3 grams of Nalco-1042 colloidal silica were added dropwise and the resulting mixture was stirred for approximately 4 hours. To this mixture, 89.1 grams of Optalake 2130f-2 (A-8), a colloidal metal oxide, were added dropwise and the resulting mixture was stirred overnight to yield a coating composition. A solution consisting of 3.8 grams of DCDA dissolved in 77.1 grams of PMOH were added to the above coating composition. After stirring for almost one complete day, 23 hours, 0.3 grams of a PA-57 solution, 10% PA-57 in PMOH, were added to the composition and allowed to stir for 10 to 30 minutes. This coating composition was applied to etched ADC lenses, ADC plaques and 1.7 R[0066] _Iplaques, according to the procedure above, at a withdrawal rate of 2 ipm to provide a cured coating having a thickness of about 2.0 microns, a refractive index of about 1.60, and a Bayer number of 5.7. After exposure to boiling tap water tint for 15 minutes, the coated lenses or plaques did not exhibit any crazing.

Comparative Ex. B

26.6 grams of GPTMS were added dropwise to a stirring 40.2 grams of deionized water. The aqueous-organic GPTMS mixture was stirred for 1 hour. A solution of 4.6 grams of itaconic acid dissolved in 40.2 grams of PMOH were added quickly to the aqueous GPTMS mixture followed by 30 minutes of stirring. 16.8 grams of TEOS were added dropwise and the resulting mixture was stirred overnight. To this mixture, 44.3 grams of Optalake 2130f-2 (A-8), a colloidal metal oxide, were added dropwise and the resulting mixture was stirred for an additional 4 hours to yield a coating composition. [0067]

Comparative Ex. B1

0.14 grams of a flow modifier comprising a PMOH-based solution containgin 10 weight percent PA-57, were added to 190 grams of the coating composition, as described in comparative example B. The coating composition was left to stir for an additional 10 to 30 minutes to insure mixing. This coating composition was applied to etched ADC lenses, ADC plaques and 1.7 R[0068] _Iplaques, according to the procedure above, at a withdrawal rate of 2 ipm to provide a cured coating having a thickness of about 1.9 microns, a refractive index of about 1.60, and a Bayer number of 6.5. After exposure to boiling tap water tint for 10 minutes, the coated lenses or plaques exhibited crazing.

Comparative Ex. B2

1.9 grams of DCDA were added to 190.0 grams of the coating composition, as described in comparative example B. The mixture was left to stir for approximately 4 hours followed by the addition of a 0.14-gram solution of PA-57, 10 weight percent in PMOH. The coating composition was left to stir for an additional 10 to 30 minutes to insure mixing. This coating composition was applied to etched ADC lenses, ADC plaques and 1.7 R[0069] _Iplaques, according to the procedure above, at a withdrawal rate of 2 ipm to provide a cured coating having a thickness of about 1.9 microns, a refractive index of about 1.60, and a Bayer number of 7.1. After exposure to boiling tap water tint for 15 minutes, the coated lenses or plaques did not exhibit any crazing.

Example 5

56.3 grams of GPTMS were added dropwise to a stirring solution composed of 9.5 grams of 0.05N aqueous HCl solution. The aqueous-organic GPTMS mixture stirred for approximately 30 minutes. A solution of 9.6 grams of ITA dissolved in 203.1 grams of PMOH were added quickly to the mixture and stirred for an additional 30 minutes. To the mixture, 17.7 grams of TEOS were added to the mixture and stirred for approximately 5 hours. 10.2 grams of Nalco-1050 colloidal silica were added dropwise and the resulting mixture was stirred overnight. To this mixture, 93.6 grams of Optalake 2130f-2 (A-8), a colloidal metal oxide, were added dropwise and the resulting mixture was stirred for an additional 4 hours to yield a coating composition. [0070]

Example 5A

1.4 grams of a flow modifier comprising a PMOH-based solution containing 10 weight percent FC-430 (3M), were added to 190 grams of a coating composition prepared in accordance with the process described in Example 5. The coating composition was left to stir for an additional 10 to 30 minutes to insure mixing. This coating composition was applied to etched ADC lenses, ADC plaques and 1.7 R[0071] _Iplaques, according to the procedure above, at a withdrawal rate of 2 ipm to provide a cured coating having a thickness of about 1.7 microns, a refractive index of about 1.61, and a Bayer number of 2.3. After exposure to boiling tap water tint for 15 minutes, the coated lenses or plaques did not exhibit any crazing.

Example 5B

1.9 grams of DCDA were added to 188.1 grams of the coating composition, as described in Example 5, followed by a dilution with 7.3 grams of a 50 weight percent solution of PMOH in deionized water. The mixture was left to stir overnight followed by the addition of a 1.4 gram solution of FC-430 (3M), 10 weight percent in PMOH. The coating composition was left to stir for an additional 10 to 30 minutes to insure mixing. This coating composition was applied to etched ADC lenses, ADC plaques and 1.7 R[0072] _Iplaques, according to the procedure above, at a withdrawal rate of 2 ipm to provide a cured coating having a thickness of about 1.5 microns, a refractive index of about 1.61, and a Bayer number of 6.2. After exposure to boiling tap water tint for 15 minutes, the coated lenses or plaques did not exhibit any crazing.

Example 6

56.1 grams of GPTMS were added dropwise to a stirring solution of 9.5 grams of a 0.05N aqueous HCl solution. The aqueous-organic GPTMS mixture stirred for approximately 30 minutes. A solution of 9.6 grams of ITA dissolved in 198.9 grams of PMOH were added quickly to the mixture and stirred for an additional 30 minutes. To the mixture, 17.7 grams of TEOS were added to the mixture and stirred for approximately 4 hours. 15.0 grams of Nalco-1042 colloidal silica were added dropwise and the resulting mixture was stirred overnight. To this mixture, 93.3 grams of Optalake 2130f-2 (A-8), a colloidal metal oxide, were added dropwise and the resulting mixture was stirred for an additional 4 hours to yield a coating composition. After exposure to boiling tap water tint for 15 minutes, the coated lenses or plaques did not exhibit any crazing. [0073]

Example 6A

1.4 grams of a flow modifier comprising a PMOH-based solution containing 10 weight percent FC-430 (3M), were added to 190 grams of a coating composition prepared in accordance with the process described in Example 6. The coating composition was left to stir for an additional 10 to 30 minutes to insure mixing. This coating composition was applied to etched ADC lenses, ADC plaques and 1.7 R[0074] _Iplaques, according to the procedure above, at a withdrawal rate of 2 ipm to provide a cured coating having a thickness of about 1.3 microns, a refractive index of about 1.61, and a Bayer number of 5.0. After exposure to boiling tap water tint for 15 minutes, the coated lenses or plaques did not exhibit any crazing.

Example 6B

1.7 grams of DCDA were added to 188.3 grams of the coating composition, as described in example 6, followed by a dilution with 6.0 grams of a 50 weight percent solution of PMOH in deionized water. The mixture was left to stir overnight followed by the addition of a 1.4 gram solution of FC-430 (3M), 10 weight percent in PMOH. The coating composition was left to stir for an additional 10 to 30 minutes to insure mixing. This coating composition was applied to etched ADC lenses, ADC plaques and 1.7 R[0075] _Iplaques, according to the procedure above, at a withdrawal rate of 2 ipm to provide a cured coating having a thickness of about 1.6 microns, a refractive index of about 1.61, and a Bayer number of 5.8. After exposure to boiling tap water tint for 15 minutes, the coated lenses or plaques did not exhibit any crazing.

Comparative Ex. C

63.7 grams of GPTMS were added dropwise to a solution composed of 27.5 grams of 0.01N aqueous HCl, 46.9 grams of methanol, 101.9 grams of methylethyl ketone, and 12.2 grams of ITA. The aqueous-organic GPTMS mixture was stirred for 1 hour. 56.0 grams of TEOS were added dropwise and the resulting mixture was stirred overnight. To this mixture, 91.8 grams of Optalake 1130F-2(A-8), a colloidal metal oxide, were added dropwise and the resulting mixture was stirred for an additional 7 hours to yield a coating composition. [0076]

Comparative Ex. C1

0.95 grams of L-77 were added to 190 grams of the coating composition, as described in comparative example C. The coating composition was left to stir for an additional 10 to 30 minutes to insure mixing. This coating composition was applied to etched ADC lenses, ADC plaques and 1.7 R[0077] _Iplaques, according to the procedure above, at a withdrawal rate of 2 ipm to provide a cured coating having a thickness of about 1.3 microns, a refractive index of about 1.61, and a Bayer number of 4.0. After exposure to boiling tap water tint for 10 minutes, the coated lenses or plaques exhibited crazing.

Comparative Ex. C2

2.4 grams of DCDA were added to 187.6 grams of the coating composition, as described in comparative example C. The mixture was left to stir overnight followed by the addition of 0.96 grams of L-77. The coating composition was left to stir for an additional 10 to 30 minutes to insure mixing. This coating composition was applied to etched ADC lenses, ADC plaques and 1.7 R[0078] _Iplaques, according to the procedure above, at a withdrawal rate of 2 ipm to provide a cured coating having a thickness of about 1.4 microns, a refractive index of about 1.60, and a Bayer number of 7.6. After exposure to boiling tap water tint for 10 minutes, the coated lenses or plaques exhibited crazing.

Comparative Ex. D

A stirred mixture of 63.6 grams of GPTMS and 56.0 grams of TEOS were added dropwise to 27.5 grams of a 0.01N HCl solution. Stirring proceeded for approximately 1 hour followed by the addition of a solvent mixture of 46.9 grams of methanol and 101.9 grams of methylethyl ketone. After the mixture was stirred for 1 hour, the resulting composition was aged in the cold room, 4 C, for approximately 24 hours. To this mixture, 91.8 grams of Optalake 1130F-2(A-8), a colloidal metal oxide, were added dropwise and the resulting mixture was stirred overnight. 12.2 grams of ITA were added to the mixture and stirred for an additional hour to yield a coating composition. [0079]

Comparative Ex. D1

0.95 grams of L-77 were added to 190 grams of the coating composition, as described in comparative example D. The coating composition was left to stir for an additional 10 to 30 minutes to insure mixing. This coating composition was applied to etched ADC lenses, ADC plaques and 1.7 R[0080] _Iplaques, according to the procedure above, at a withdrawal rate of 2 ipm to provide a cured coating having a thickness of about 1.2 microns, a refractive index of about 1.61, and a Bayer number of 4.6. After exposure to boiling tap water tint for 10 minutes, the coated lenses or plaques exhibited crazing.

Comparative Ex. D2

2.4 grams of DCDA were added to 187.6 grams of the coating composition, as described in comparative example D. The mixture was left to stir for 1 hour followed by the addition of 0.96 grams of L-77. The coating composition was left to stir for an additional 10 to 30 minutes to insure mixing. This coating composition was applied to etched ADC lenses, ADC plaques and 1.7 R[0081] _Iplaques, according to the procedure above, at a withdrawal rate of 2 ipm to provide a cured coating having a thickness of about 1.5 microns, a refractive index of about 1.60, and a Bayer number of 6.0. After exposure to boiling tap water tint for 10 minutes, the coated lenses or plaques exhibited light crazing.
Thus, it should be apparent that there has been provided in accordance with the present invention a coating composition and a method for making and using same that fully satisfy the objectives and advantages set forth above. Although the invention has been described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art. Accordingly, it is intended to embrace all such alternatives, modifications and variations that fall within the spirit and broad scope of the appended claims. Changes may be made in the construction and the operation of the various components, elements and assemblies described herein and changes may be made in the steps or the sequence of steps of the methods described herein without departing from the spirit and scope of the invention as defined in the following claims. [0082]

Claims

What is claimed:

1. A coating composition which, when applied to a substrate and cured, provides an abrasion resistant coating on the substrate and has a refractive index, comprising:

an aqueous organic solvent mixture containing hydrolysis products and partial condensates of an epoxy functional silane, a colloidal silica material, a metal oxide composite colloid, a tetrafunctional silane, and a carboxylic acid functional compound, wherein the carboxylic acid functional compound is selected from the group consisting of monofunctional carboxylic acids, multifunctional carboxylic acids, anhydrides, and combinations thereof, and further wherein the epoxy functional silane is present in a molar ratio to the colloidal silica component, the tetrafunctional silane component, and the metal oxide composite colloid component of from about 0.05:1 to 2:1 and the molar ratio of the colloidal silica component and the tetrafunctional silane component to the metal oxide composite colloid component is from about 0.01:1 to about 50:1.

2. The coating composition of claim 1, wherein the hydrolysis products and partial condensates of the epoxy functional silane are present in the aqueous-organic solvent mixture in an amount from about 10 to about 90 weight percent based on the total solids of the composition.

3. The coating composition of claim 1, wherein the carboxylic acid functional compound is present in the aqueous-organic solvent mixture in an amount of from about 1 to 90 weight percent, based on the total weight of the composition.

4. The coating composition of claim 1, wherein the colloidal silica component is present in the aqueous-organic solvent mixture in an amount of from about 0.1 to 70 weight percent, based on the total solids of the composition.

5. The coating composition of claim 1, wherein the metal oxide composite colloid component is present in the aqueous-organic solvent mixture in an amount of from about 0.1 to 80 weight percent, based on the total solids of the composition.

6. The coating composition of claim 1, wherein the tetrafunctional silane component is present in the aqueous-organic solvent mixture from about 0.1 to 70 weight percent, based on the total solids of the composition.

7. The coating composition of claim 1, wherein the solvent constituent of the aqueous-organic solvent mixture is selected from the group consisting of an alcohol, an ether, a glycol ether, an ester, a ketone, a glycolether acetate and combinations thereof.

8. The coating composition of claim 1, wherein the solvent constituent of the aqueous-organic solvent mixture is an alcohol having the general formula ROH, where R is an alkyl group containing from about 1 to about 10 carbon atoms.

9. The coating composition of claim 1, wherein the solvent constituent of the aqueous-organic solvent mixture is selected from the group consisting of a glycol, an ether, a glycol ether and mixtures thereof having the formula R¹—(OR²)_x—OR¹where x is an integer of 0, 1, 2, 3, or 4, R¹is H or an alkyl group containing from about 1 to about 10 carbon atoms, and R²is an alkylene group containing from about 1 to about 10 carbons atoms and combinations thereof.

10. The coating composition of claim 1, wherein the epoxy functional silane is represented by the formula R⁴ _xSi(OR⁵)_4-xwhere x is an integer of 1, 2 or 3, R⁴is H, an alkyl group, a functionalized alkyl group, an alkylene group, an aryl group, an alkyl ether, and combinations thereof containing from 1 to about 10 carbon atoms and having at least 1 epoxy functional group, and R⁵is H, an alkyl group containing from 1 to about 5 carbon atoms, an acetyl group, a —Si(OR⁶)_3-yR⁷ _ygroup where y is an integer of 0, 1, 2, or 3, and combinations thereof, R⁶is H, an alkyl group containing from 1 to about 5 carbon atoms an acetyl group, another —Si(OR⁶)_3-yR⁷ _ygroup and combinations thereof, and R⁶is H, an alkyl group, a functionalized alkyl group, an alkylene group, an aryl group, an alkyl ether and combinations thereof containing from 1 to about 10 carbon atoms.

11. The coating composition of claim 1, wherein the carboxylic acid functional compound is represented by the formula R⁸(COOR⁹)_x; where x is an integer of 1, 2, 3, or 4, and further R⁸is H, an alkyl group, a functionalized alkyl group, an alkylene group, an aryl group, a functionalized aryl group, an alkyl ether, and combinations thereof containing from 1 to about 10 carbon atoms, and R⁹is H, a formyl group, a carbonyl group, or an acyl group, where the acyl group can be functionalized with an alkyl group, a functionalized alkyl group, an alkylene group, an aryl group, a functionalized aryl group, an alkyl ether, and combinations thereof containing from 1 to about 10 carbon atoms, and where R⁸and R⁹may or may not be joined by a chemical bond.

12. The coating composition of claim 1, wherein the metal oxide composite colloidal component may contain any combination of alumina, silica, titania, zirconia, tin oxide, antimony oxide, iron oxide, lead oxide, and/or bismuth oxide, and further wherein at least one of the metal oxide components present in the composite mixture is neither alumina nor silica.

13. The composition of claim 1 wherein the colloidal silica component is either acidic, basic, or neutral.

14. The coating composition of claim 13, wherein the colloidal silica component is an acidic colloidal silica component.

15. The coating composition of claim 1, wherein the tetrafunctional silane is represented by the formula Si(OR¹⁰)₄where R¹⁰is H, an alkyl group containing from 1 to about 5 carbon atoms and ethers thereof, an (OR¹⁰) carboxylate, a —Si(OR¹¹)₃group where R¹¹is H, an alkyl group containing from 1 to about 5 carbon atoms and ethers thereof, an (OR¹¹) carboxylate, another —Si(OR¹¹)₃group and combinations thereof.

16. The coating composition of claim 1, wherein the amount of water present in the aqueous-organic solvent mixture is an amount sufficient to provide a substantially homogeneous mixture of hydrolysis products and partial condensates of all reactive components.

17. The coating composition of claim 16, further comprising an effective amount of co-hydrolysis catalyst thereby enhancing the hydrolysis rates of the hydrolyzable components.

18. The coating composition of claim 1, further comprising an effective amount of a catalyst to thereby providing enhanced abrasion resistance to a cured coating.

19. The coating composition of claim 18, wherein the effective amount of the catalyst is from about 0.01 to about 2 weight percent, based on the total solids of the composition.

20. The coating composition of claim 1, wherein the aqueous-organic solvent mixture further comprises an effective amount of a leveling agent thereby spreading the aqueous-organic solvent mixture on the substrate to provide substantially uniform contact of the aqueous-organic solvent mixture with the substrate.

21. The coating composition of claim 1, wherein the aqueous-organic solvent mixture further comprises from about 0.1 to about 50 weight percent, based on the total solids of the composition, of a mixture of hydrolysis products and partial condensates of a silane additive represented by the formula R¹² _xSi(OR¹³)_4-xwhere x is an integer of 1, 2 or 3, R¹²is H, an alkyl group containing from 1 to about 10 carbon atoms, a functionalized alkyl group, an alkylene group, an aryl group an alkyl ether group and combinations thereof, R¹³is H, an alkyl group containing from 1 to about 10 carbon atoms, an acetyl group and combinations thereof.

22. The coating composition of claim 21, wherein the amount of water present in the aqueous-organic solvent mixture is an amount sufficient to provide a substantially homogeneous mixture of hydrolysis products and partial condensates of all reactive components.

23. The coating composition of claim 22, further comprising an effective amount of co-hydrolysis catalyst thereby enhancing the hydrolysis rates of the hydrolyzable components.

24. The coating composition of claim 20, further comprising an effective amount of a catalyst thereby providing enhanced abrasion resistance the cured coating.

25. The coating composition of claim 24, wherein the effective amount of the catalyst is from about 0.01 to about 2 weight percent, based on the total solids of the composition.

26. The coating composition of claim 20, wherein the aqueous-organic solvent mixture further comprises an effective amount of a leveling agent thereby spreading the aqueous-organic solvent mixture on the substrate to provide substantially uniform contact of the aqueous-organic solvent mixture with the substrate.