DE2309777A1 - COMPOSITIONS FOR COATING GLASS - Google Patents

Description

DART IKDUSTRIES INC., Los Angeles, California, U.S.A. "Compositions for coating glass"

The invention relates to polymer coatings, processes for their production and those provided with these polymer coatings Articles and in particular polyethylene coatings, processes for their manufacture and glassware, such as bottles containing such Polyethylene coatings have been provided.

It has long been known to provide glassware with polymer coatings. These coatings were mostly used for protection which uses glass substrates against surface abrasion and frictional stress. These abrasions not only worsen the appearance of the outer surface of the glassware, but also reduce their breaking strength. The well-known coatings show brittleness mainly and especially at low temperatures. Usually they are in the form of thin films that are firmly connected to the glass surface and fully adhere to it. These coatings are thereby of Disadvantage that the coatings as well as the glassware break easily if they are dropped. Furthermore, if that The glass vessel is under overpressure, as is the case with bottles, for example.

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ORIGINAL INSPECTED

that are filled with carbonated beverages, such as sodas, beer or sparkling wine, cause the glass to break that the glass fragments are violently thrown over considerable distances. Thus make the above coatings the glassware is not "shatterproof", nor does it change the fracture properties of the breakable, overpressured glassware in a noticeable way.

With regard to the last-mentioned properties, it should be noted that that these glass objects, in particular glass spray bottles, have been provided with polymeric protective covers. Of these it is stated that they are resistant to the shards of glass that result from breaking or shattering. These materials however, in the majority of cases they are not suitable for applications on glass. For example, most have coatings of this type a thickness which, for economic reasons alone, prohibits its use in other areas. Furthermore, the appearance these thick coatings are generally not so satisfactory that they can be used on glass articles used in the food industry and the beverage industry. Furthermore, these coatings do not have the properties that their use on bottles allow the strict cleaning and Treatment steps are subjected to depending on the type of product to be filled.

The above-mentioned disadvantages are eliminated by providing a glass substrate, such as a glass container, with an elastic, provides a non-brittle, resin-like coating into which at least one compound is incorporated which has functional groups, that react with groups that appear on the surface of the

Glass substrate are present, such as silanol groups (-Si-OH), and keeping the number of functional groups in the coating high enough to be relatively uniform, however partial adhesion of the coating from the glass substrate is achieved as opposed to complete adhesion of the coating in those cases where the corresponding reactive groups are present in large amounts. Due to the partial detention

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At least of the coating on the glass substrate, breakage of the glass substrate will cause the coating to peel away therefrom and in the the area immediately surrounding the break is stretched. In the case of breakage of containers under low or low If there is no excess pressure, the coating usually remains intact and envelops the broken and released fragments of glass.

When bottles that are under internal overpressure break, the contents of the bottle begin to escape through the opening. At the same time, the sharp tips of the glass pierce the coating at the point of break, so that the overpressure is reduced will. The cracks in the glass layer or the glass break point spread from the break point to other areas the bottle. The coating separates from the glass above these fractures and expands to the extent that the glass breaks, and holds the glass fragments together on both sides of the break line, while the overpressure escapes completely through the opening initially formed. In this way it is prevented that broken glass violently thrown around those in the vicinity Injure or damage people or property. In normal use, the coating adheres uniformly on the glass substrate, even if it is irregularly shaped, such as in areas provided with letters of glass bottles etc. Similarly, the adhesive properties not affected by filling under heat, by washing with lye or by pasteurization.

According to the invention, the objects are therefore provided with an elastic, provided non-brittle, partially adherent coating, which is produced according to a multi-stage process, according to a mixture of a polyethylene base resin with a 'low, up to a medium density with a melt index below ICO and a fundamental viscosity number (intrinsic viscosity) of more than 0.5 with an acidic polymeric material, such as an oxidized polyolefin or wax, and Po-

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lymeren is mixed that contain ethylenically unsaturated carboxylic acids or anhydrides. The mixture obtained should be a Have an acid number of at least 0.5, preferably below 20, and contain at least 60% by weight of the base resin. As polyethylene base resins, homopolymers and various copolymers, such as ethylene / vinyl acetate copolymers, and as acidic polymeric materials, particularly oxidized polyethylene and materials that include acrylic acid and / or maleic anhydride.

The compound having the functional groups can be incorporated into the coating material in various ways e.g. by interpolymerization with one or more monomers, by graft polymerization onto the polymer Materials, by chemically changing the polymeric materials or by physically mixing a suitable one Base resin with a polymeric material containing the compound having the functional groups, such as by Mixing melts or powders.

According to a preferred embodiment of the invention relates to this is a coating material and glass objects provided therewith, which is produced by physically mixing a polyethylene base resin with at least one acidic polymeric material such as an oxidized polyolefin, an oxidized wax or a Polymer containing an ethylenically unsaturated carboxylic acid or an ethylenically unsaturated acid anhydride is obtained became. The concentration of the base resin in the mixture of the base resin and the acidic polymeric material should be at least 60% by weight, preferably at least 80% by weight. The relative amounts of the base resin and the acidic polymeric material are selected such that the acid number of the total Coating material is at least 0.5, whereby adequate partial adhesion of the coating material to the glass is achieved. In order to prevent too strong adhesion, the acid number should not exceed about 20, whereby the

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The number is preferably kept in a range from about 1 to about 15 should be. The acid number is determined by the method used to determine the acid number of fatty acids is and stands for the amount of potassium hydroxide in milligrams that is used to neutralize one gram of the substance to be examined Material is needed. The determination is carried out by titrating an alcoholic solution of the material with Alkali using phenolphthaline as an indicator (ASTM method No. D198O-67).

The ethylenically unsaturated acidic monomer of the polymeric material can be a monocarboxylic acid, a polycarboxylic acid or an acid anhydride, preferably having 3 to 8 carbon atoms per molecule, or the material can be a partial ester of a polycarboxylic acid or a mixture of two or be more of the aforementioned acidic compounds. Examples of such acidic monomers are acrylic acid, methacrylic acid, Ethacrylic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, Vinyl sulfonic acid, maleic anhydride and monomethyl and monoethyl esters of maleic acid and fumaric acid. The polymer Material can be a homopolymer or a copolymer the above-mentioned compounds with one or more other monomers, such as low molecular weight α-olefins, e.g. Ethylene, propylene, butene-1, or vinyl monomers such as styrene, vinyl acetate, esters of acrylic acid or methacrylic acid and the like Be connections.

Examples of polymeric materials used in the present invention are polyacrylic acid and copolymers containing it, such as ethylene / acrylic acid copolymers, ethylene / methacrylic acid copolymers, Ethylene / ethacrylic acid copolymers, ethylene / crotonic acid copolymers, ethylene / fumaric acid copolymers, Ethylene / maleic acid copolymers, ethylene / itaconic acid copolymers, ethylene / vinylsulfonic acid copolymers, Ethylene / maleic anhydride copolymers, ethylene / maleic acid monomethyl ester copolymers, Ethylene / maleic acid monoethyl ester copolymers,

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Ethylene / monomethyl fumarate copolymers and monoethyl ethylene / fumarate copolymers. Examples of materials of this type used according to the invention are also given the copolymers of low molecular weight α-01efinen, which are different from ethylene and 3 to 6 carbon atoms in the Molecule with any acidic monomers of the type described above, e.g. copolymers containing propylene, butene-1, Contain 3-methylbutene-i or 4-methylpentene-1. Other examples suitable copolymers are terpolymers of two different a * -olefins and one of the abovementioned acidic monomers as well as terpolymers of an oc-olefin with one of the acidic monomers mentioned above and a vinyl compound, such as vinyl acetate, vinyl chloride, vinyl alcohol, vinyl ether, vinyl fluoride and the like.

The compounds given above and the processes for their preparation are known, so that not in the following will be discussed further.

The polyethylene base resin with which the aforementioned acidic polymeric materials are mixed should be a material which has a significant amount of short side chains in addition to long side chains, so that it becomes elastic and high Has elongation and great tensile strength at break. This resin can be a homopolymer or a copolymer of ethylene with at least one other comonomer, which results in further short side chains on the main polymer chain, be. Examples of suitable comonomers are other than ethylene α-01efine, e.g. propylene, butene-1, 3-methylbutene-1, 4 — methylpentene-1, vinyl compounds such as styrene, vinyl esters Vinyl ethers, vinyl chloride, vinyl fluoride and vinyl alcohols, vinylidene compounds such as vinylidene chloride or vinylidene fluoride, Esters, such as ethyl or vinyl esters of acrylic acid, Methacrylic acid, substituted methacrylic acid, crotonic acid, ilaconic acid, maleic acid or fumaric acid, acrylonitrile, fumaric acid acid dinitrile, acrylamides, vinylene carbonate, carbon monoxide and

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other similar compounds. The comonomer content of this base resin should be relatively low, generally below about 20% by weight, preferably in a range from about 2 to about 7% by weight, in order to ensure that the resin does not become too rubbery and the tensile strength at Breakage and maximum elongation are above the lower limits of about 70.3 kg / cm ² (1000 psi) and about 200 %, respectively. In the case of low molecular volume comonomers such as carbon monoxide, vinyl fluoride, vinylidene fluoride and vinyl alcohol, the broad upper limit can be increased to about 50% by weight. By increasing the comonomer content from 0 % to the maximum possible value, a corresponding increase in the clarity of the base resin is achieved, which extends from an opaque state to a substantially clear state. Furthermore, such an increase generally leads to a corresponding lowering of the melting point and, consequently, of the temperature which is required for the subsequent application of the coating material to the glass substrate. Thus, the incorporation of a comonomer into the polyethylene base resin reduces or prevents destruction of the coating material as a result of excessively high treatment temperatures. The comonomer content extends as a function of the particular properties which the coating to be achieved is to have and is also influenced by other variables such as the type of comonomer, the composition of the acidic polymeric material and the percentage of this acidic polymeric material in the mixture . According to the invention is a random copolymer of, ethylene and vinyl acetate whose vinyl acetate content between about 2 and about 7 wt .-%, based on the base resin, is particularly _(suitable.

A requirement of the above-mentioned polyethylene resins is that their melt index is determined according to the ASTM method Mr. D-1238i does not exceed 100 and preferably below is about 10. Furthermore, the density of the material,

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■ determined according to ASTM method No. D-1505, not higher than about 0.94-5 and is preferably between about 0.915 and held about 0.930. Third, the intrinsic viscosity of this material should be at least 0.5 dl / g, best according to Sem / ASTM method D-1601 (oc-chloronaphthalene at 125 ° C) and is preferably kept between about 0.65 and about 0.90 dl / g. If these three criteria are adhered to at the same time, the base resin shows a high elasticity and toughness, which is reflected in a tensile strength at breakage of at least 70.3 kg / cm (1000 psi) (determined according to ASTM method No. D-638) and a highest elongation of at least 200% (determined according to ASTM method No. D-638 at 20 inches per minute).

The Pc used in the invention "^ athylengrundharze any conventional procedures, for example, can be described in the US Patent 3,293,233, at pressures of about 1000 atmospheres to about 3000 atmospheres and temperatures in the range of about 90 ⁰ C to about 300 ⁰ C using in the presence of peroxide catalysts The reaction is normally carried out using a relatively narrow temperature range within the broad operating temperature range set forth above.

Then under conditions which ensure that the acidic polymeric material is substantially uniform in the mixture is dispersed, appropriate amounts of the polyethylene base resin mixed with the acidic polymeric material. Here Conventional methods such as mixing melts or powders or a combination of these two methods can be used will. It is also within the scope of the invention to incorporate the acidic polymeric material into the coating by it in the form of a thin layer on the surface of polyethylene base resin particles deposited, for example, by mixing the polyethylene base resin, which is in particle form, with the acidic impregnated polymeric material, which in a suitable solution

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medium is dissolved, whereupon the material is dried to remove the solvent.

Comprises a "particularly" preferred embodiment of the invention a coating made by mixing the powdery ingredients has been obtained for a sufficient time in a known device necessary for the formation of a uniform Mixture of the coating material is suitable. After applying the coating material to the surface of the glass objects, followed by a curing step, the resulting coating adheres particularly good at the places where particles have been deposited on the glass surface, which the acidic polymer Contain material while in the areas where particles of polyethylene base resin are deposited on the glass surface adhere with considerably less strength. In this way a coating is obtained that is uniform but punctiform adheres to the glass surface and which separates from the glass in a defined manner when the glass breaks, whereby the glass object becomes "shatterproof".

Although it is not important to achieve "split crochet" security is whether the adhesion sites of the coating to the glass are uniformly in clusters, as seen with powder mixtures achieved, with each acidic polymer particle forming such a cluster, or non-uniformly in clusters are arranged, as it can be done by applying a coating material, that was obtained by melt blending, achieved on the glass substrate, there is a clear advantage over Coatings obtained by mixing powders in that the amount of acidic polymeric material can be decreased for a given degree of adhesion. This is especially true for mixtures containing the acidic polymer Contains material in a smaller particle size than the polyethylene base resin. Thus, the preferred acid grade should be of the coating material, when obtained by a powder-egg bed process, in a range from about 1 to 9 lie.

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If desired, various dyes, pigments and / or fillers are incorporated into the mixtures in order to achieve certain coloring and / or surface effects. E.g. can in the case of coating materials which have been mixed by fusing, the dye is added by first adding produces a dye concentrate, e.g. a mixture of dry pigments and / or dyes with a suitable one Carrier material, such as a polyethylene, with a relatively high melt index of e.g. 20. Then a small amount of the concentrate produced by fusing it with the coating mixture mixed, extruded, milled and on a suitable Particle size sieved. In the case of powder mixtures, the colorant can be used in the manner described above before Mix to be added to each of the ingredients. On the other hand, the pigments and / or dyes can be used directly in dry form, in the form of a paste, a colloidal dispersion in mineral oil or water or as a dye solution to the Mixture added and then mixed in, preferably using high-energy mixing devices. Mixing devices such as Henshel mixers, countercurrent mixers or ball mills can be used.

The particle size of the final coating obtained using any of the conventional powder application methods applied should generally be between about 0.062 mm to about 0.69 mm (25 mesh to 250 mesh Tyler screen), preferably between about 0.188 mm and about 0.4-2 mm (35 to 70 mesh). Therefore, a grinding process is used conventional methods with the help of devices developing shear and impact effects and subsequent sieving of the ground Materials required to have a final coating material to obtain desired particle size. These procedural measures can be carried out before or after the components of the coating material are mixed.

The final coating material finally obtained is then under

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Any "known application method" is applied to the glass substrate, for example by emulsion application, spray application, electrostatic application and fluidized bed application. After application, the coating is cured under the necessary conditions Conditions are selected such that only a relatively thin layer of the resilient coating is applied, generally the coating thickness is about 5 to about 90 percent of the thickness of the glass substrate, the preferred range being from about 5 to about 50 percent. The minimum coating thickness should be at least 0.005 cm (0.002 inches).

In certain cases it may be desirable to increase the lubricity of the coating. This can be achieved, for example be that the coated article is provided with a very thin final coating of a suitable material or a Lubricant incorporated directly into the coating material using methods such as those described above for incorporating Dyes, pigments or fillers have been described.

Examples of coated glass articles according to the invention include Containers such as bottles and glasses, incandescent light bulbs, flash bulbs, television picture tubes, laminated safety glass and the like

The following examples, in which commercially available beverage bottles have been coated with various particulate materials, using a fluidized bed application process. In all cases the coating materials were removed prior to placement in the swirl chamber, which is equipped with facilities for filling a swirling gas with a relatively low superficial velocity was provided, whereby a dense, non-turbulent fluidized bed was achieved, to a particle size of ' 0.4-2 mm ($ 5 mesh Tyler screen) crushed and sieved. then

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beverage bottles were (0.090 inches), which were obtained from Thatcher Glass Manufacturing Company, preheated with an average wall thickness of about 0.229 cm to a temperature in the range of about 218 to about 246 ° C (425 to 4-75 ⁰ F), then are introduced into the fluidized bed for 2 to 5 seconds by coating them with thicknesses of about 0.015 cm to about 0.041 cm (0.006 to 0.016 inches) and then for 4 to 6 minutes in a curing oven at temperatures between about 218 to about 246 ⁰ C (425 to 475 ° F) hardened,

whereupon they were allowed to cool for at least 24 hours prior to examination. The coated bottles were then examined for surface appearance and adhesion of the coating to the glass. The appearance of the surface was rated "poor" or "good", with a "poor" rating being given if the coating had stains and blisters. With respect to the adhesion study, the samples were rated _r are numbers from 1 to 5, the surrendered as follows:

1. Cover easily removable - smooth inner surface of the Coating

2. Cover difficult to peel off - rough inner surface

3. Coating splinters, cannot be peeled off

4. The coating is difficult to chip off

5. The coating is very difficult to chip off.

The bottles were then pressurized to about 4.57 atmospheres (65 psig) with carbonated water, sealed, and examined for "splinter resistance". These tests were performed using a container that had a square concrete floor measuring 1.31 * <■ 1.31 m (4x4 feet), clear plastic walls (Lucit) with a height of 1.31 m (4 feet) and a clear one Cover made of the same material with a central opening, which had such a large diameter that the bottles to be examined could be pushed through the opening onto the concrete

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fall to the ground. 3uesen could. The "splinter security" was according to of the definitions given below as poor, medium, good and excellent:

bad - the bottle breaks into at least 3 to 4 pieces, whereby the top of the bottle breaks and the smooth parts of the bottle can fly away;

medium - in certain cases the bottle will break into 3 to 4 pieces, in other cases it will keep its shape and the longitudinal axis of the bottle has a crack;

good - the bottle keeps its shape, keeping all the pieces together, although a break seam may extend across 3/4 of the bottle;

The bottle retains its shape, with only a break at the bottom, from which the pressure escapes and no cracking occurs.

Examples 1 to 6

These comparative examples explain the effect of the acid number and the content of the base resin of the coating material on the appearance, the adhesion and the splinter resistance. A random copolymer of 97% by weight ethylene and 3% by weight vinyl acetate with a density of 0.924, a melt index of 0.9, an intrinsic viscosity of 0.84, a tensile strength at break of about 134 kg was used as the polyethylene base resin / cm (19ΟΟ psi) and a maximum elongation of 620 % . A copolymer of 6% by weight acrylic acid and 94% by weight ethylene with an acid number of 46.7 was used as the acidic polymeric material. Powder mixtures were prepared which contained 5, 10, 15 and 20% by weight of the ethylene / acrylic acid polymer and the bottles were coated with these mixtures as well as with 100% polyethylene base resin and 100% ethylene / acrylic acid polymer. The experimental values obtained in these investigations are given in Table I below.

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- 14 Table I.

Ex.
No. Reason-
resin
Wt% sour butt
lymerisat
Weight % Acid-
number liability Splinter
safety Appearance 1 100 0 0 1 out
draws bad 2 95 5 2.34 cvj out
draws Well 3 90 10 4.67 3 Well Well 4th 85 15th 7.01 4th Well Well 5 80 20th 9.34 4th middle Well 6th 0 100 46.7 5 bad Well

Examples 7 and 8

Using the base resin used in Examples 1-5 Powder mixtures were produced, "in which an ethylene / acrylic acid copolymer An acrylic acid content of 15% by weight was used. Example 7 "passed the mix from 99% by weight of the base resin and 1% by weight of the acrylic acid copolymer, while in Example 8 these weight percentages were 96 "and 4, respectively. The experimental results obtained Results are summarized in Table II below.

Table II

Ex.
Fr. reason
resin
Wt% sour butt
lymerisat
Wt% Acid-
number liability Splinter
safety Appearance 7th 99 1 1.17 2 out
draws Well
i 8th 96 4th 4.67 3 Well Well

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Example 9

Bottles with a mixture of 96% by weight of the previous examples used base resin and 4% by weight of an ethylene / acrylic acid copolymer coated, the one Acrylic acid concentration of 20 wt .-%.

The acid number of the mixture obtained was 6.22. The subsequent Examination of the bottles that had been coated with the powder mixture found a "good" appearance, one "good" splinter resistance and a liability rating of 4-.

Example 10

A mixture was produced which contained 90% by weight of the ethylene / Vinyl acetate base resin of Examples 1 to 5 and 10% by weight of one Styrene / methacrylic acid polymer containing 7 wt .-% Methacrylic acid included. The acid number of the mixture was 4.6. The examination of the bottles coated with this material showed that the coatings resulted in good splinter resistance, gave an adhesion rating of 2 and a had a good surface appearance.

Examples 11 to 12

The ethylene / vinyl acetate copolymer base resin used in Examples 1 to 5 was in a weight ratio of 99 ϊ 1 with an ethylene / maleic anhydride copolymer (1: 1 molar ratio of ethylene and maleic anhydride) mixed, resulting in a mixture with an acid number of 8.9 resulted.

Another mixture was prepared in the same way, with the difference that the acidic copolymer used was an ethylene / maleic acid copolymer (Molar ratio 1: 1) was used, resulting in an acid value of 7 * 8. The investigation of the bottles coated with these materials resulted in improved adhesion and a better surface appearance coatings compared to coatings made from 100% of the base resin. The splinter protection was excellent

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draws.

Examples 15 to 14-

These comparative examples show the effect of the acid number on the adhesion of the coating, the base resin being an ethylene homopolymer with a melt index of 1.0, a density of 0.921, a tensile strength at break of about 127 kg / cm ² (1800 psi), a maximum elongation of 500 % and a basal molar

both viscosity number of 0.83 was used. There are bottles / with the base resin as well as with a powder mixture of 90 wt, -% of Äthylenhomopolymerisats with 10 wt -.% Of an oxidized polyethylene having an acid number of about 15 (American Cyanamid AC-629) to obtain a mixture having an acid number of about 1.5 received, coated. The comparative tests showed that the coating containing no oxidized polyolefin had poor adhesion (rating 1) and a poor surface appearance, particularly on the base and the labeled areas of the bottles, while the coating mixture adhered uniformly (rating 2), a good appearance Surface and develops a medium protection against splintering.

Example 15

In this example, a mixture obtained by melting of 1% by weight of polyacrylic acid and 99% by weight of an ethylene / Vinyl acetate copolymer produced. The copolymer contained 5% by weight vinyl acetate, had a density of about 0.926, a melt index of about 20, an intrinsic viscosity

number of about 0.8 dl / g, a tensile strength of about 123 kg / cm (175Ο psi) and a maximum elongation of 720 %. The mixture was extruded, ground and sieved to a particle size of 0.4-2 mm (35 mesh Tyler screen). The bottles coated with this material showed excellent splinter resistance, good appearance and resulted in an adhesion rating of

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Claims (25)

Claims 1. Polymer compositions, characterized in that they contain at least 60% by weight of a polyethylene base resin a melt index of no more than about 100, one basolar Intrinsic viscosity of at least about 0.5 dL / g and a density of no more than about 0.94-5 and at least one acidic polymeric material, such as an oxidized polyolefin, an oxidized wax or a polymer, the one Contains ethylenically unsaturated carboxylic acid or an ethylenically unsaturated carboxylic acid anhydride, the relative amounts of the polyethylene base resin and the acidic polymeric material are selected such that the acid number of the coating material is at least 0.5. 2. Compositions according to claim 1, characterized in that that the acid number has a value from about 1 to about 15. 3. Compositions according to claim 1, characterized in that that the mixture consists of a powder mixture whose acid number is between about 1 and about 9. 4. Compositions according to claim 1, characterized in that that the polyethylene base resin is an ethylene homopolymer. 5- compositions according to claim 1, characterized in that that the polyethylene base resin is a random copolymer of ethylene and vinyl acetate. ■ "> 6. Compositions according to claim 1, characterized in that the acidic polymeric material is an oxidized polyolefin is. 309837/1077 7. Compositions according to claim 1, characterized in that that the acidic polymeric material consists of an ethylenic unsaturated carboxylic acid ". 8. Compositions according to claim 1, characterized in that the acidic polymeric material is a copolymer from an α-olefin and an ethylenically unsaturated carboxylic acid or an ethylenically unsaturated calcium anhydride is. 9.. Compositions according to claim 1, characterized in that that the acidic polymeric material is a styrene / methacrylic acid copolymer is. 10. Compositions according to claim 5 »characterized in that that the vinyl acetate is used in an amount of about 2 to about 7% by weight, based on the base resin. 11. Compositions according to claim 1, characterized in that that the acidic polymeric material is a polyacrylic acid. 12. Compositions according to claim 8, characterized in that the acidic polymeric material is a copolymer of ethylene and an ethylenically unsaturated carboxylic acid or an ethylenically unsaturated carboxylic acid anhydride. 13. Compositions according to claim 12, characterized in that the acidic polymeric material is an ethylene / maleic acid copolymer is. 14. Compositions according to claim 12, characterized in that the acidic polymeric material is an ethylene / maleic anhydride copolymer is. 15 compositions according to claim 12, characterized in that that the acidic polymeric material is an ethylene / acrylic acid 3098 3 7/1077 re-copolymer is. 16. Compositions according to claim 15, characterized in that that the polyethylene base resin is an ethylene / vinyl acetate copolymer is. 17 · Process for the production of a material suitable for the formation of coatings on a glass substrate, characterized in that, that one has a polyethylene base resin having a melt index of no more than about 100, an intrinsic viscosity of at least about 0.5 and a density of no more than about 0.94-5 in an amount of at least 60% by weight with at least an acidic polymeric material such as an oxidized polyolefin, an oxidized wax or a polymer, the one Ethylenically unsaturated carboxylic acid or an ethylenically unsaturated one Contains carboxylic anhydride, mixed in such a way that the mixture has an acid number of at least 0.5. 18. The method according to claim 17, characterized in that the polyethylene base resin and the acidic polymeric material before after mixing to particle sizes of about 0.062 mm to about 0.69 mm (25 to 250 mesh). 19 · The method according to claim 17, characterized in that the mixture to a particle size of about 0.062 mm to about 0.69 mni (25 to 250 mesh) is crushed. 20. The method according to claim 18, characterized in that the particle sizes about 0.188 mm to about 0.42 mm (35 "to 75 mesh). 21. The method according to claim 19, characterized in that that the particle size ranges from about 0.188 mm to about 0.42 mm (35 "to 75 mesh). 22. Glass objects provided with an elastic, resin-like coating, obtained according to a method which is 309837/1077 is to use a polyethylene base resin having a melt index of no more than about 100, an intrinsic viscosity of at least about 0.5, and a density of no more than about 0.945 with at least one acidic polymeric material, such as an oxidized polyolefin, an oxidized wax or a polymer that is an ethylenically unsaturated carboxylic acid or contains an ethylenically unsaturated carboxylic acid anhydride, mixed, wherein the amount of polyethylene base resin in the mixture is at least about 60 wt .- ^ and the relative Amounts of the polyethylene base resin and the acidic polymeric material are selected so that the acid number of the obtained Mixture is at least 0.5. 23 · Glass objects according to claim 22, characterized in that the mixture is a powder mixture whose Acid number is about 1 to about 9. 24. Glass articles according to claim 22, characterized in that the thickness of the coating is at least about 0.005 cm (0.002 inches) and is about 5 to about 90 % of the thickness of the glass substrate. 25. Glass articles according to claim 24, characterized in that the thickness of the coating is about 5 to about 50 % of the thickness of the glass substrate. 309837/1077