Fatty ethenoid acylaminoorganosilicon compounds and their use in compositions for coating glass

The instant invention relates to the use of acylaminoorganosilicon compounds in compositions to enhance the surface properties of glass articles with the exception of glass fibers.

In US-A-2,929,829 and 2,928,858 Acylaminoorganosilicon compounds are described. These acylaminoorganosilicon compounds were considered useful as, among other things, acid-base indicators; additives for silicon products, such as oils and gums; thermosetting resins for coating materials; and ultraviolet ray absorbers.

Subsequent to said work, improvements based on acylaminoorganosilicon compounds were discovered. In U.S.-A- 3,249,461, the use of conjugated olefin containing acylaminoorganosilicon compounds was taught as effective fiber glass reinforcing agents. In U.S. - A - 3,681,266, a distinct class of acylaminoorganosilicon compounds was fluorine modified to provide a coating material that is useful as a water repellant. In U.S. - A - 3,720,699, a new and useful class of haloorganoacylaminoorganosilicon compounds are reported to be useful as a coating material.

A variance on the theme, U.S. - A - 3,755,354 is directed to amide acid and imido-substituted organosilicon compounds that are reportedly useful as glass fiber coupling agents. In a closely related U.S. - A - 3.787,439, imido-substituted organopolysiloxanes were disclosed, including conjugated, unsaturated acylaminoorganosilicon compounds, as additives for glass fibers.

In U.S. - A - 3,959,327, acylaminoorganosilicon compounds with thio-containing substituents were reported as plasticizers and coupling agents.

A new class of complex acylaminoorganosilicon compounds was reported in U.S. - A - 4,209.455 and 4,284,548. In each the mono- and bis-silanes were characterized by a single acylamino group and at least one secondary or tertiary aminoorgano group. These compositions were considered useful in fiber sizes.

In U.S. - A - 3,746,738, acylaminoorganosilicon compounds that contained various pendant silanes were described as useful glass fiber sizes.

In U.S. - A - 3,537,832, silylated polymers were prepared by amidation of acid chloride modified polymers with aminoorganosilanes for use as coating materials.

CA 84:59633W teaches stearoyl and oleoyl acylaminoorganosilicon compounds.

In EP-0 136 680, filed on 28.9.1984 and claiming a priority of 30.9.83 acylaminoorganosilicon compounds containing fatty ethenoid groups are described as useful glass fiber sizes.

It is well known in the art that glass derives its strength from an unblemished surface and any scratches or flaws which are present on the surface decreases the strength of the glass many-fold. Glass articles, such as bottles, sheets and fibers possess their maximum strength shortly after they are formed. Their strength rapidly diminishes when they are subjected to abrasive contact in the course of handling, packaging and shipping.

This problem is illustrated for glass containers that are used by processors of food and beverages. The glass containers are subjected to a number of processing operations. The containers are washed, filled, closed, labelled and packaged for delivery. During these operations, the glass containers are rubbed or otherwise contacted in various ways, often under high pressure, which can cause scratching. The glass containers repeatedly come into contact with each other as they move from station to station and during the various washing, filling, closing and packaging operations. Although the need for a glass protective coating was described for glass containers, there are other applications in which this coating for glass articles will be useful.

Numerous references to compositions and materials used as protective coatings exist in the patent literature for glass surfaces. The most widely used protective coatings, for glass bottles, include tin and titanium compounds such as titanium and stannic halides and alkyl titanates. These materials are sprayed on the surface of the glass at a temperature of from 480°C to 640°C. The tin and titanium compounds are believed to react with moisture in the air to form a TiO₂ or SnO₂ layer. After the glass is annealed to about 230°C or lower, a second coating that consists of a polyethylene emulsion, is applied as described in U.S. - A - 2,995,533, 3,598,632, 3,496,825, 3,853,612 and 4,272,587. The coating system described in these patents provide a very good protective finish to the glass surface. The coating, however, is very expensive. The price of the intermediates, such as the stannic halide or titanium compounds, the two step application, and the damage to the metal equipment resulting from the corrosive nature of the metal halides all contribute to the unit cost of this coating.

Protective aqueous coating compositions consisting of an organofunctional silane and an organic polymer, such as, for example, vinyl polymers (U.S. Patent No. 3,998,985), polyamino-acrylate esters (U.S. - A - 4,224,365 and 4.250,068) and epoxy (U.S. - A - 4,056,208, EP - A1 - 57 595) are either difficult to apply, i.e. require a primer coat, costly or do not possess the combination of properties required for the glass application, such as for bottles.

Attempts to circumvent the above problems consisted of coating the glass surfaces with an aqueous emulsion of an olefin such as polyethylene and a silane, such as polyethyleneaminepropyltrimethoxysilane or an ethylenediaminopropyltrialkoxysilanes, (U.S. - A - 3,873,353) or a alkyltrialkoxysilane, (U.S. - A - 3,801,361) or gamma-aminopropyltriethoxysilane, (U.S. - A - 4,130,677) or simply an aqueous solution of a silane and an amine salt of acetic acid, (U.S. - A - 3,438,801). While good abrasion resistance and "labelability" are alleged for these coatings, the adhesion of the coating to the bottle when subjected to an aqueous wash, especially aqueous caustic wash, is too low for certain applications.

It is an object of this invention that special acylaminoorganosilicon compounds together with a dispersing agent and a fatty acid and optionally a polymer in combination with an aqueous emulsion of organic polymer, or with an organic solvent and/or water is used as coating composition to yield improved balance between the various glass surface properties, including labelability, appearance, abrasion resistance (wet/dry scratch), lubricity and durability to caustic wash over existing coatings that contain an organofunctional silane; the coating compositions do not generate toxic, corrosive or obnoxious fumes.

In accordance with the present invention, coating compositions for glass articles, as defined in claim 1 are provided.

DETAILED DESCRIPTION OF THE INVENTION

The fatty ethenoid acylaminoorganosilicon compounds represented by formula I above can be prepared by a variety of known techniques. The basic reaction is the acylation of an aminoorganosilane by reaction with a carboxylic organic acid, a carboxylic organic acid halide, an ester or anhydride derivative of a carboxylic organic acid. The aminoorganosilanes suitable for acylation are represented by the formula: <chemistry id="chem0001" num="0001"><img file="EP0146142B1_D0001.tif" /></chemistry> wherein Y and W are as defined in claim 1 but excluding <chemistry id="chem0002" num="0002"><img file="EP0146142B1_D0002.tif" /></chemistry> and X, R, R¹, R², b, c, x, y and z are as defined in claim 1. At least one Y must be -R⁵Si(OR⁶)_3-a(R⁷)_a and at least one other Y must be hydrogen.

Preferably, the aminoorganosilanes are such that R and R¹ are ethylene or propylene, R² is methyl or hydrogen, R⁵ is propylene, R⁶ and R⁷ are methyl or ethyl, a=0 or 1, b=0 or 1, c=1, x=1 to 4, y=0 to 3 and z=0 or 1.

Suitable acylation reagents are those represented by the general formula <chemistry id="chem0003" num="0003"><img file="EP0146142B1_D0003.tif" /></chemistry> where R⁴ is a monovalent hydrocarbon group containing anywhere from 8 to 24 carbon atoms and at least one double bond and X is a halogen atom, a hydroxyl group, an ester group (-OR⁸) or an anhydride group (-OCOR⁹). Wherein R⁸ and R⁹ are monovalent hydrocarbon groups.

The free fatty acid is converted to the acylation reagents by well known techniques. For instance, when X is to be halogen, the fatty acid is converted at room temperature or higher by simple addition of thionyl halide to the fatty acid and thereafter removal of sulfur dioxide and hydrogen chloride is effected. If an fatty acid ester is desired, it is obtained by catalyzed esterification with alcohols and fatty acid and removal of byproduct water. If the anhydride derivative is desired the anhydride derivative is produced by catalyzed dehydration of the fatty acid. Most, if not all, of these acylation reagents are commercially available.

The details as to the acylation reaction conditions between the monoprimary and/or secondary aminosilane and the carboxylic organic acid or derivative are more fully set forth in U.S. - A - 2,929,829

where monoaminoorganosilicon compounds are reacted with carboxylic organic acid halides, a tertiary alkyl amine, such as Et₃N or pyridine may be employed to remove the HX and aid the completion of the acylaminoorganosilicon compound. In other instances an excess of aminoorganosilicon compound instead of the tertiary alkyl amine or pyridine is used to produce a mixture of aminoorganosilicon hydrogen halide and the corresponding fatty ethenoid acylaminoorganosilicon compound. In this latter approach the aminoorganosilicon hydrogen halide compounds remain as a water compatible co-reactive silane component which in some instances may provide a substantial benefit to end use handling and performance of the coating for glass articles.

For many coating applications it is preferred to use carboxylic acid chloride acylating reagents because they are readily available, highly reactive and least complicated by undesirable side reactions. Optional removal of HCl is sometimes advantageous.

Aminoorganosilanes having 2 or more amino groups and one or more silane groups are reacted with carboxylic organic acid halide to obtain a fatty ethenoid acylaminoorganosilicon compound which can have a combination of fatty acylamino, free amino and amine hydrogen halide groups as well as one or more silane groups.

Once again, reference is made to U.S. - A - 2.929.829 for particulars relative to reaction conditions.

For production of water dilutable coatings from polyaminoorgano(poly)silanes, it is preferred to add carboxylic acid chloride slowly to a well stirred solution of silane in methanol, ethanol or the like at from 0° to 150°C preferably 25-70°C. The in situ formation of aminoorgano hydrogen halide salt groups which occurs during this reaction provides the product with water solubility or dispersibility. This preferred process for fatty ethanoid acylated derivatives of polyaminoorgano(poly) silane compounds generally is used to produce the same molar concentration of acylated amine and amine hydrogen halide salt groups. The molar concentration of free amino groups will largely depend on the extent of acylation initially undertaken in this process and can vary widely.

The compounds used according to this invention are complex structures, but can be produced by alternate methods. In one such method a polyalkyleneamine is reacted with the carboxylic organic acid, its acid halide or anhydride to provide a partial acylamino derivative, which is also an amino containing intermediate that is subsequently silylated by conventional means to provide the acylaminoorganosilicon compound desired.

This process has a tendency to produce higher viscosity products with varying amounts of polysiloxane product in place of the full amount of silane ester groups. Subsequent dilute aqueous dispersions also show a somewhat greater tendancy to destabilize with time.

In general, it is prefered to silylate polyalkyleneamines according to the teachings of U.S. - A - 3,746,738 and to subsequently acylate as previously described.

In all of the reactions set forth above the desired end product is a fatty ethenoid acylaminoorganosilicon compound represented by the general formula: <chemistry id="chem0004" num="0004"><img file="EP0146142B1_D0004.tif" /></chemistry>

Preferably, the fatty ethenoid acyl aminoorganosilicon compounds are such that R and R¹ are alkylene radicals and more preferably ethylene or propylene. R² is methyl or hydrogen, R⁴ is a hydrocarbon radical containing 8 to 24 carbon atoms and at least one double bond, R⁵ is propylene, R⁶ and R⁷ are methyl or ethyl, a=0 or 1, b=0 or 1, c=1, x=1 to 4, y=0 to 3 and z=0 or 1, and at least one Y is -R⁵Si(OR⁶)_3-a(R⁷)_a and at least one other Y is <chemistry id="chem0005" num="0005"><img file="EP0146142B1_D0005.tif" /></chemistry>

Exemplary of the fatty ethenoid acylaminoorganosilicon compounds are set forth in Table I below: <tables id="tabl0001" num="0001"><img file="EP0146142B1_D0006.tif" /></tables>

The fatty ethenoid acylaminoorganosilicon compounds is used in combination with a dispersing agent, such as, an organic solvent and/or water. The organic solvent can be any of those commonly used to dissolve or disperse organic coatings, including alcohols, ketones, esters, ethers and the like. These solvents are useful as a vehicle for applying the fatty ethenoid acylaminoorganosilicon compounds to the glass surface. A preferred composition comprises from 0.01 to 20 weight percent of the fatty ethenoid acylaminoorganosilicon compounds dissolved or dispersed into water. As prepared, it may be applied as hereinafter described. It is an aspect of the instant invention to use a three component coating composition as claimed in claim 13.

The organic polymer that can be used in combination with the fatty ethenoid acylaminoorganosilicon compounds can be a polyolefin including polyethylene, polypropylene; polyisobutylene; a polyether including polyethylene oxide, polypropylene oxide, and polyethylene oxide polypropylene oxide copolymer; and an epoxy or other polymer that imparts a waxy nature to the coating. A preferred composition comprises forming an aqueous emulsion of the polyolefin. Details for preparing this preferred emulsion are set forth in U.S. - A - 2,995,533.

The fatty acids that can be used in combination with the fatty ethenoid acylaminoorganosilicon compounds are principally derived from the body fat of animals, such as lard and tallow; from fruit pulp, such as palm and olive; the seed of plants, such as cottonseed, peanut, corn, safflower, sesame, sunflower, rapeseed, mustardseed, soybean and linseed.

It should not be construed to mean the acids are derived solely from non-petroleum materials.

Preferably, the fatty acid contains 8 to 18 carbon atoms: more preferably the fatty acids are stearic acid, oleic acid and/or linolenic acid.

The coating composition for glass articles is prepared by dissolving from 0.01 to 20 weight percent fatty ethenoid acylaminoorganosilicon compounds into water and then dissolving, dispersing or emulsifying from 0.01 to 50 weight percent fatty acid and optionally polymer.

Preferably, the coating for glass articles is prepared by dissolving from 0.05 to 3 weight percent fatty ethenoid acylaminoorganosilicon compounds into water and then adding 0.05 to 5 weight percent polyolefin in the form of an aqueous emulsion, as described in U.S.-A-2,995,533.

Another aspect of the instant invention is a two step coating process for glass articles in which 0.01 to 20 weight percent solution of fatty ethenoid acylaminoorganosilicon compounds is deposited into the glass surface in one application step followed by depositing the fatty acid and optionally the polymer in a subsequent application step.

In the first application step, the fatty ethenoid acylaminoorganosilicon compounds are deposited from an aqueous or organic solution. The organic solvents can be any of those commonly used to dissolve or disperse organic coatings, including alcohols, ketones, esters, ethers, and so on. These solvents are useful as a vehicle for applying the class of fatty ethenoid acylaminoorganosilicon compounds to the glass surface. A preferred composition comprises from 0.05 to 3 weight percent of the fatty ethenoid acylaminoorganosilicon compound dissolved into water.

In the second application step, the organic polymer that is dispersed in an organic solvent and/or water can be a polyolefin including polyethylene; polypropylene; polyisobutylene; a polyether including polyethylene oxide, polypropylene oxide, polyethylene oxide polypropyleneoxide copolymer; and an epoxy or other polymer that imparts a waxy nature to the coating.

Preferably, the organic polymer is applied as an aqueous emulsion of from 0.05 to 5 weight percent polyethylene, as described in U.S. - A - No. 2,995,533.

The fatty acids that can be deposited on the glass surface in the second application step are the some as those which have been previously described.

The coatings for glass articles described in the instant invention can be applied by any techniques commonly known in the art of coatings including spraying, dipping, wiping, brushing and misting.

A preferable method for applying the coatings is to spray a solution of the coatings described in the instant invention onto a glass surface that is at a temperature between 90°C and 250°C.

Although not wishing to be bound by any specific limits on the amount of coating necessary to enhance the surface properties of the glass articles, it is advisable to employ at least 0.1 mg of the coating per cm² of the surface area of the glass article, with approximately 1.5 mg coating/cm² being preferred. It should be noted that at the lower coating levels, higher concentrations of the fatty ethenoid acylaminoorganosilicon compound is recommended if a two or three component coating system is employed.

The following specific examples illustrate certain aspects of the present invention and, more particularly, point out methods of evaluating the same. All parts and percentages are by weight unless otherwise specified. For the purposes of these examples Me denotes a methyl group.

Production of Fatty Ethenoid Acylaminoorgano Compounds: <ul id="ul0001" list-style="none"><li>A.) Into a 1 liter, 3-necked flask equipped with dropping funnel, thermometer, thermosensor, mechanical stirrer, heating mantle, 324 mm (1 foot 3/4") O.D. Vigreaux column, distillation head and receiver was charged 85.3 g (0.25 moles) of [(MeO)₃SiCH₂CH₂CH₂]₂NH, 35.4 g (0.35 moles) of triethylamine and 194.5 g of toluene. Starting at room temperature, through the dropping funnel was added to the stirred mixture 74.2 g , (0.25 moles)of linseed acid chloride. An exotherm resulted throughout the addition and the reaction mixture temperature was held between 30° and 50°C by external application of a water/ice bath. After an additional hour of stirring at ∼35°C the total reaction mixture was pressure filtered through a 1µm filter pad and the resulting Et₃N ^. HCl salt cake was washed with three 50 ml portions of toluene. The combined filtrate and toluene extract of the salt cake were vacuum stripped to 100°C/l,33 mbar pressure to remove toluene, excess triethylamine and any other low boiling components. ¹³C, and ²⁹Si NMR indicate the product structure is <chemistry id="chem0006" num="0006"><img file="EP0146142B1_D0007.tif" /></chemistry> linseed acid chloride derivative).</li><li>B.) In much the same equipment setup as described in A 85.3 g ( 0.25 moles) of [(MeO)₃Si(CH₂)₃]₂NH was stirred at 50°C while 37.11 g (0.125 moles)of linseed acid chloride was slowly added through a dropping funnel. An exotherm resulted throughout the addition and external cooling was used to control the reaction temperature between 50° and 60°C. The reaction mixture analyzed for 0.98 meq/gm chloride ion [96% of theoretical]. ¹³C and ²⁹Si, NMR indicate an equimolar mixture of <chemistry id="chem0007" num="0007"><img file="EP0146142B1_D0008.tif" /></chemistry> a linseed acid chloride derivative) and [(MeO)₃SiCH₂CH₂CH₂]₂NH · HCl.</li><li>C.) In the same equipment setup described in A 76.8 g (0.2 moles)of [(MeO)₃SiCH₂CH₂CH₂NHCH₂]₂ dissolved in 106.7 g (3.33 moles)of methanol was charged. The homogeneous mixture was stirred at room temperature and 29.7 g (0.10 moles)of linseed acid chloride was slowly added. An exotherm resulted throughout the addition and air cooling was used to control the reaction temperature between 50° and 60°C. The reaction mixture was heated to reflux methanol for one hour, cooled and analyzed for chloride ion [98.3% of theoretical]. The product mixture at 50 wt.% active in methanol, had a calculated average composition: <chemistry id="chem0008" num="0008"><img file="EP0146142B1_D0009.tif" /></chemistry><chemistry id="chem0009" num="0009"><img file="EP0146142B1_D0010.tif" /></chemistry></li><li>D.) In much the same manner as described in C , 76.8 g (0.2 moles)of [(MeO)₃SiCH₂CH₂CH₂NHCH₂]₂ dissolved in 136.4 g (4.26 moles)of methanol was reacted with 59.4 g (0.20 moles)of linseed acid chloride. The resulting product, at 50 wt. % active in methanol, has a calculated average composition: <chemistry id="chem0010" num="0010"><img file="EP0146142B1_D0011.tif" /></chemistry></li><li>E.) In much the same manner as described in A 76.8 g . (0.2 moles)of [(MeO)₃SiCH₂CH₂CH₂NHCH₂]₂_, 50.6 g (0.5 moles)of triethylamine and 250 g of toluene was reacted with 118.7 g (0.4 moles)of linseed acid chloride to give the corresponding di("fatty" ethenoid acylamino)organo-bis-silane <chemistry id="chem0011" num="0011"><img file="EP0146142B1_D0012.tif" /></chemistry></li><li>F.) In much the same manner described for C 265.4 g (1.0 mole)of NH₂CH₂CH₂NHCH₂CH₂NH(CH₂)₃Si(OMe)₃ dissolved in 562.4 g of methanol was reacted with 297 g (1.0 moles)of linseed acid chloride to produce the corresponding "fatty" ethenoid acylamino hydrochloride derivative with the average composition: <chemistry id="chem0012" num="0012"><img file="EP0146142B1_D0013.tif" /></chemistry> where R⁴ is a linseed acid chloride derivative.</li><li>G.) In much the same manner described in C 222.1 g (1.0 moles) of NH₂CH₂CH₂NH(CH₂)₃Si(OMe)₃, dissolved in 519.1 g , of methanol, was reacted with 297 g (1.0 moles)of linseed acid chloride to produce the corresponding "fatty" ethenoid acylamino hydrochloride derivative with the average composition:</li></ul><chemistry id="chem0013" num="0013"><img file="EP0146142B1_D0014.tif" /></chemistry>

Example 1

To 98.1 parts water are added 0.4 parts of the "fatty" ethenoid acylamino organosilicon compound that is illustrated by the formula; C₁₇H₂₉CONHCH₂CH₂NHCH₂CH₂NHCH₂CH₂Si(OCH₃)₃ · HCl which is dissolved in methanol (50 weight percent). After the pH is adjusted to 11.52, 1.5 parts of aqueous emulsion of polyethylene that is 20% solids by weight is added with stirring at room temperature. The preparation of the polyethylene emulsion is disclosed in U.S. - A - 2,995,533.

The test results for the aqueous mixture of 0.2 weight percent <chemistry id="chem0014" num="0014"><img file="EP0146142B1_D0015.tif" /></chemistry> and 0.3 weight percent solid polyethylene are given in Table II , Compound 1. Also shown in Table II are the commercial coatings and representative mixtures of 0.2 wt. percent acylaminosilanes, which do not belong to the "fatty" ethenoid acylaminosilicon compounds and 0.3 weight percent polyethylene. <tables id="tabl0002" num="0002"><img file="EP0146142B1_D0016.tif" /></tables><tables id="tabl0003" num="0003"><img file="EP0146142B1_D0017.tif" /></tables>

Bottle Coating Procedure

Test bottles are washed with acetone and heated in an oven to 565°C for at least 4 hours to clean the glass surface, and then cooled to 177°C. The bottles are then removed from the oven and immediately suspended from the shaft of an electric motor that is rotating at 50 rpm and are sprayed with the aqueous emulsion of the "fatty" ethenoid acylaminoorganosilicon compound and the polyethylene for 3 revolutions. A Devilbiss spray gun, Model #EGA-502 set for a fan pattern and siphon feed using 1.38 bar (20 psi) air pressure is used. The distance between the spray gun nozzle and the glass bottle is 457 mm (18 in). This spraying technique deposits approximately 0.037 g/cm² of the aqueous emulsion onto the glass surface. The coating quickly dries to form a clear, colorless film. The bottle is then removed and allowed to cool to room temperature before the bottles are tested.

Testing Procedures

1.)

Scratch Test

Scratch resistance is measured on a laboratory scale static load tester. The device slides the surfaces of two bottles together at 45° under constant load. Load settings can be varied from 4.5 to 45 kg (10 to 100 pounds). The bottles pass at a particular load setting if no nicks are seen in the area of the test. Bottles are tested both wet and dry. In the wet test, the bottles are sprayed with a fine mist of water just prior to the test.

2.)

Lubricity Test

Lubricity is expressed in terms of slip angle. Slip angle is measured on a motorized tilting table (manufactured by the American Glass Research Corporation). Three coated bottles are arranged in a pyramid on their sides on the table. The 2 bottom bottles are held in place and the third allowed to move. The table is tilted at a slow constant rate until the top bottle slips approximately 6,35 µm (1/4"). The angle at the point of slippage between the plane of the bottom of the 2 bottles and the horizontal is measured and recorded as the slip angle.

3.)

Label Adhesion

The test method for determining label adhesion is performed in accordance with ASTM method D-3359-58. The labels are first coated with an adhesive - 51 to 76 µm at room temperature. The application is done by means of a wet film knife ( 127 µm wet). The bottles, affixed with labels, are heated at 60°C for 20 minutes. After cooling to room temperature, a crosscut of 6,35 mm is made at an angle of 90° on the label. The grid area is examined to determine the extent of label adhesion as follows: <dl id="dl0001"><dt>0</dt><dd>(less than 50% of label remains on bottom after crosscut)</dd><dt>1</dt><dd>(-50% of label remains on bottle after crosscut)</dd><dt>2</dt><dd>(75% of label remains on bottle after crosscut)</dd><dt>3</dt><dd>(90% of label remains on bottle after crosscut)</dd><dt>4</dt><dd>(95% of label remains on bottle after crosscut)</dd><dt>5</dt><dd>(100% of label remains on bottle after crosscut)</dd></dl> A total of three crosscuts are made at random areas on the label with the average classification reported.

4.)

Aqueous Caustic Wash

The aqueous caustic wash consists of submerging a bottle into 70°C, 5% by weight sodium hydroxide solution for 30 minutes, and then thoroughly rinsed with distilled water.

5.)

Appearance

A qualitative judgment of the coating's appearance is made by shining a bright light on the bottle in a dark room.

Examples 2 to 10

The coating compositions Nos. 2 to 10 are made, applied and tested as described above. Although the dry scratch resistance after caustic wash for coating compositions Nos. 2 to 10, (Table III) are less than for the first coating in Table II, the adhesion of common adhesives (casein, Vinyl Dex™, polyvinyl acetate and jelly gum) is considerably better, especially for coating No. 6 and 9 (Table III). <tables id="tabl0004" num="0004"><img file="EP0146142B1_D0018.tif" /></tables><tables id="tabl0005" num="0005"><img file="EP0146142B1_D0019.tif" /></tables>

Examples 11-13

To 98 parts water are added varying amounts of <chemistry id="chem0015" num="0015"><img file="EP0146142B1_D0020.tif" /></chemistry> After the pH is adjusted to 11.5, 1.5 parts of an aqueous emulsion of polyethylene that is 20% solids by weight is added with stirring at room temperature. The preparation of the polyethylene emulsion is disclosed in U.S. - A - . 2,995.533. The coating and testing procedures are described in Example 1. Data are given in Table IV. <tables id="tabl0006" num="0006"><img file="EP0146142B1_D0021.tif" /></tables>

Examples 14-19

To 98 parts water is added 0.5 parts <chemistry id="chem0016" num="0016"><img file="EP0146142B1_D0022.tif" /></chemistry> After the pH is adjusted to 11.5, 1.5 parts of an aqueous emulsion of polyethylene that is 20% solids by weight is added with stirring at room temperature. The preparation of the polyethylene emulsion is disclosed in U.S. - A - 2,995,533. The coating and testing procedures are described in Example 1, except that the temperature of the glass surface is varied during the spraying operation. Data are given in Table V. <tables id="tabl0007" num="0007"><img file="EP0146142B1_D0023.tif" /></tables>

Examples 20-23

Into 99 parts water is added 1 part fatty ethenoid acylaminoorganosilicon compound and the pH is adjusted to 7 (Solution A).

Into 98.5 parts water is added 1.5 parts aqueous emulsion of 20% solids polyethylene. The preparation of the polyethylene emulsion is disclosed in U.S. - A - 2,995,533 (Solution B).

Bottle Coating Procedure

Test bottles are washed with acetone and heated in an oven to 565°C for at least 4 hours to clean the glass surface, and then cooled to 177°C. The bottles are then removed from the oven and immediately suspended from the shaft of an electric motor that is rotating at 50 rpm and are sprayed with Solution A for 3 revolutions. A Devilbiss spray gun, Model #EGA-502, set for a fan pattern and siphon feed using 1.38 bar (20 psi) air pressure is used. The distance between the spray gun nozzle and the glass bottle is 45.7 mm (18 in). Within 1 minute, the glass bottles are sprayed with Solution B under similar conditions as that used for spraying Solution A. The bottle are allowed to cool and then they were tested according to the procedures outlined in Example 1. Data are given in Table VI . <tables id="tabl0008" num="0008"><img file="EP0146142B1_D0024.tif" /></tables>

Examples 24-31

(Comparative Examples)

Into 99 parts water is added 1 part of the fatty ethenoid acylaminoorganosilicon compound. The bottle is coated and tested as described in Example 1. <tables id="tabl0009" num="0009"><img file="EP0146142B1_D0025.tif" /></tables><tables id="tabl0010" num="0010"><img file="EP0146142B1_D0026.tif" /></tables>