Reaction Product of Polyalkylene Imine and Epoxy, Halo, Ethylenic Substituted Difunctional Compounds

When a surface is at a temperature on or below the dew point of the prevailing atmosphere, water condenses on the surface in the form of small droplets. When the condensation is on transparent or reflecting surfaces it is referred to as "fogging." This problem of fogging is critical for some applications and at least troublesome for many others. Substrates of plastic, glass, and metal surfaces all fog without some modification. Many attempts have been made to reduce or eliminate the fogging problem particularly for automobile windshields and safety goggles. Early attempts included the application of films containing glycerol and more recently coatings based on hydroxy substituted acrylic polymers have been offered (see U.S. Pat. No. 3,488,215 issued to Shepherd et al.) Other coatings offered to reduce the fogging of surfaces include films containing surfactants and more recently U.S. Pat. No. 3,411,945 issued to Chao describes the incorporation of surfactants in the thermoplastic polymer substrate to reduce the tendency towards fogging of the surface.

Accordingly, it is an object of the present invention to provide a non-fogging surface that does not interfere with the transparency or reflectance of the substrate material. An additional object is to provide a transparent, non-fogging coating with improved permanence of the anti-fogging protection, increased adhesion to the substrate, improved scratch and abrasion resistance, improved durability of the adhesion to the substrate and improved durability of the surface of the coating.

An additional object is to provide a transparent coating that will reduce the fogging characteristics for transparent or reflecting surfaces that may be easily applied to the surfaces to provide consistent results. A more specific object is to prepare a transparent, non-fogging coating for transparent or reflecting surfaces of glass, plastic or metal. An object is to provide anti-fogging eye lenses and protective shields, windows and mirrors.

An additional object is to provide a transparent anti-fogging coating for transparent substrates, particularly polycarbonate, with improved permanence and abrasion resistance. A more specific object is providing a novel composition of matter that is hard, resistant to detergent solutions and adheres to substrates while imparting anti-fogging characteristics.

The present invention is an anti-fogging coating, composition comprising a polyalkylene imine (e.g. polyethylene imine) cross-linked with a compound having at least two reactive groups capable of reacting with the amine hydrogen or yielding a covalent linkage to form a quaternary amine salt, to form a hard, durable, hydrophilic coating. When applied to most substrates, the degree of cross-linking is preferably high, such that sufficient cross-linking functional compound is added capable of cross-linking the films to attain water insolubility. For certain substrates, pendant reactive groups are optionally reacted to the amine hydrogens of the polyalkylene amine, the pendant groups being highly polar to promote adhesion to the substrate.

The composition of this invention provides a hard coating which is resistant to abrasion. The coating absorbs up to 50% water by weight of the coating without optical distortion or loss of adhesion to the substrate.

FIG. 1 is a view of a lens from a safety goggle;

FIG. 2 is a sectional view along the line 2--2 of FIG. 1;

FIG. 3 is a view of a mirror;

FIG. 4 is a sectional view along line 4--4 of FIG. 3;

FIG. 5 is a view of a lens;

FIG. 6 is a blow-up of a sectional view along the line of 6--6; and

FIG. 7 is a flow diagram of a method of application of the anti-fog coating of this invention to the substrate.

The substrates most useful in this invention that are normally subject to fogging include organic polymers, such as vinyl acetate polymers and polycarbonate. These polymers are commonly used for shields and goggles for industrial application where fogging can constitute a safety hazard. The coated substrates of this invention not only offer anti-fogging characteristics but also improved abrasion resistance and mechanical properties. The non-fogging materials of this invention are normally transparent although they may be tinted various colors, such as amber for ski goggles.

The polyalkylene imine useful in this invention is a well recognized class of compounds available commercially with the following repeating unit structural formula I: ##EQU1## wherein R is a substituted or unsubstituted alkylene group and n is an integer from about 2 to about 3000.

When the backbone alkylene group is ethylene, the structural formula of the repeating unit takes the form of formula II: ##EQU2## wherein R.sub.1 through R.sub.4 are chosen from the group consisting of hydrogen and lower alkyl and n is as hereinabove. It is preferred that R.sub.1 through R.sub.4 be chosen from the group consisting of hydrogen or methyl. Particularly preferred is polyethylene imine that is prepared by polymerizing ethylene imine in acid medium.

One skilled in the art will readily recognize that both formulas I and II are simplifications of the structural formula of polyalkylene imines. It is well known that this class of polymers generally forms a highly branched rather than a linear polymer structure. As a consequence, a typical structure of polyethylene imine contains a ratio of primary to secondary to tertiary nitrogens in the polymer of approximately 1:2:1. This branching does not interfere with the purposes of this invention and in fact this ratio is quite satisfactory. The formulas I and II may be considered as roughly average structures of the polymer particularly at higher molecular weights.

Although the molecular weight of the polyethylene imine polymer is not critical to the invention, the lower molecular weight range is preferred, primarily for ease of processing, handling and applying the solution to the substrate before cross-linking. The number average molecular weight (Mn) of commercially available polyethlene imine commonly ranges from about 60 (dimer) to about 120,000, and includes dipropylenetriamine, tetraethylenepentamine, etc. Preferred are polymers with average molecular weights in the range of 300 to 60,000 and most preferred is the range of 400 to 1,000.

With the higher molecular weight polyimine, the number of amine hydrogens per nitrogen atom approaches one. Theoretically, each nitrogen atom can also form a quaternary salt so that the maximum number of reactive sites per repeating unit approaches two as the molecular weight of the polyimine is increased. For the preferred lower molecular weight range the terminal groups significantly affect the number of reactive sites available for either cross-linking or attachment of pendant groups. For example, polyimine with an average molecular weight of 300 has about 7 repeating units and about 9 amine hydrogens for an average of about 1.3 amine hydrogens per repeating unit. Including the quaternary salt reaction capability brings the average number of reactive sites per repeating unit to about 2.3.

The composition of this invention is cross-linked by reaction with the amine hydrogens and/or through bonding to the nitrogen to form a quaternary ionic salt. The poly-functional compounds capable of cross-linking the imine polymer contain at least two groups capable of reacting with either the amine hydrogen or the nitrogen atom. Thus the compound may contain (1) at least two functional groups that react only with amine by hydrogens, e.g. divinyl benzene, (2) at least two functional groups capable of reacting either the amine hydrogen or the nitrogen to form a quaternary salt, e.g. methylene chloride, (3) at least one functional group capable of reacting with the amine hydrogen and at least one group capable of reacting with the nitrogen to form a quaternary salt, e.g. epichlorohydrin, or (4) at least one functional group capable of reacting with the amine hydrogen to form during the reaction a secondary functional group that in turn will react with the polyimine or with another group of like type, e.g. formaldehyde.

It is common to provide both cross-linking mechanisms in the same coating compositions, and it is also common to employ cross-linking compounds of more than one of the above groups. For example, the compounds of group (1) are particularly useful for chain extension reactions while the coating is in solution without gelling the product. Because of the branched nature of the polyalkylene imine polymers and the combination of cross-linking reactions taking place it is not known in which proportions the types of cross-linking reactions are taking place. The critical factor in the chemical compositions capable of cross-linking the polyalkylene imine polymers is that they contain at least two functional groups capable of either reacting with amine hydrogens or forming a covalent bond to a quaternary salt. References in the specification to "amine hydrogens" include both the primary and secondary nitrogen substituted hydrogen.

As a typical example, epichlorohydrin is a preferred cross-linking compound chosen from group (3) above. In this instance the cross-linking compound contains both epoxy and halogen functionality, each of which have the ability to react with the amine hydrogens on the polyalkylene imine polymers. If in the composition there are insufficient amine hydrogens to react with both the epoxy group and the halogen, the halogen can still react with the nitrogen group through the formation of a quaternary salt.

The class of functional groups capable of these reactions is well known to those skilled in the art and includes nonaromatic ethylenic unsaturation (activated unsaturation) like vinyl, vinylene, allyl, and butylene in such compounds as ethylene glycol diacrylate and dimethacrylate, glycidyl methacrylate, divinyl benzene, diallyl phthalate, triallyl cyanurate, butylene glycol diacrylate, polypropylene fumarate, allyl chloride, glycidyl methacrylate, maleic anhydride, fumaric acid, dichloromaleic anhydride, N,N'-methylene bisacrylamide, methacrylic acid, acrylic acid, 2-chloroethyl methacrylate and the like; epoxy and epithio in such compounds as diepoxides, epihalohydrin, particularly epichlorohydrin, glycidyl methacrylate, glycidol, low molecular weight epoxy resins such as the reaction product of epichlorohydrin and bisphenol -A, and the like; halo such as alkylene halide and acid halide like chloro, bromo and fluoro in such compounds as methylene chloride, methylene bromide, 1,2-dichloroethane, bis (2-chloroethyl) ether, epichlorohydrin, dichloromaleic anhydride, allyl chloride, 2-chloroethyl methacrylate, adipyl chloride; formyl and carbonyl in aldehydes and ketones in such compounds as benzaldehyde, formaldehyde, 5,5-dimethyl-1,3cyclohexadione, 2-5 hexanedione, dipentene dioxide and the like; carboxy and anhydride in such compounds as phthalic acids and anhydride, polyacrylic acid, glutaric acid, pyromellitic anhydride, methacrylic acid, acrylic acid, maleic anhydride, ethylene/maleic anhydride copolymers, and the like; isocyanato and isothiocyanato in such compounds as methylene bis(4-phenyl isocyanate and isothiocyanate); acidic hydroxy including phenolic hydroxy in such compounds as bisphenol-A and the like; and other functional groups that react directly or through intermediate reactions with either the amine hydrogens or the nitrogen atoms to form quaternary salts.

The intermediate reactions possible are numerous in that many of the cross-linking compounds form additional functional groups during the reaction with polyimine. Some of these secondarily formed functional groups may in turn react with a polyimine or more likely react with the reaction product of another reaction with the polyimine. As an example, the reaction of glycidol with the polyimine is believed to first attach through an addition reaction of the epoxy with the amine hydrogen. A secondary reaction between the two of these reaction products (each containing two hydroxyl groups) to yield a cross-link between the polyimine chains is possible, although this theory has not yet been clearly demonstrated. The term "polyfunctional" in describing the cross-linking compounds also includes those chemical compounds that through the reaction with the polyimine, form an additional functional group that reacts with the polyimine or the same functional group from another site. An example of this type of polyfunctional compound is formaldehyde with which the reaction with the amine hydrogen forms a methylol group that will in turn react with another methylol group splitting out water to cross-link the imine polymer.

The preferred novel composition of matter of this invention contains at least two of those cross-linking compounds containing two different functional groups chosen from the group consisting of epoxy, ethylenic unsaturation and halo. A preferred embodiment has one compound with epoxy and halogen functionality and a second with epoxy and ethylenic unsaturation functionality. An example of compounds containing combination of epoxy and halogen functionality is represented by the chemical structure depicted in formula III, with epichlorohydrin being particularly preferred: ##EQU3## wherein R.sub.8 is alkylene having one to eight carbon atoms, R.sub.5 to R.sub.7 are each hydrogen or lower alkyl and X is halogen.

An example of the second class of compounds containing epoxy and ethylenic functionality is represented by the chemical structure depicted in formula IV below: ##EQU4## wherein R.sub.9, R.sub.11 and R.sub.12 are each chosen from the group consisting of hydrogen and lower alkyl, and R.sub.10 is alkylene having one to four carbon atoms.

The amount of cross-linking compound reacted with the polyalkylene imine depends to a degree on the choice of cross-linking compound and the particular qualities desired in addition to the anti-fog characteristics obtained through the invention. The novel composition of matter preferably is the water insoluble resinous product comprising the reaction product of at least 15 weight percent of a polyalkylene imine, such as polyethylene imine, 10 to 40 weight percent of a chemical compound represented by formula III, such as epichlorohydrin, and 20 to 60 weight percent of a chemical compound represented by the formula IV, such as glycidyl methacrylate. Particularly preferred is the resinous reaction product of 20 to 35 weight percent polyalkylene imine, 20 to 35 weight percent formula III, and 30 to 55 weight percent formula IV.

For some uses, it is optional to add additional cross-linking monomers such as those of Group 1 described hereinabove, typically up to about 10 weight percent. It is optional to react mono-functional compounds onto the polyalkylene amine polymers that do not effectively cross-link the polymer. These mono-functional compounds react with polyimine to form groups that are generally pendant and may be particularly effective in promoting adhesion to the substrate. The adhesion promoters are preferably reacted onto the polyalkylene imine before any reaction with the cross-linking compounds. They include highly polar functional groups which promote adhesion to polymeric substrates such as polycarbonates resins, vinyl acetate polymers, acrylic polymers, and the like. These highly polar groups may be attached by any of the functional groups effective in the cross linking compounds with the criticality being that only one of those functional groups capable of reacting with the amine hydrogens be present and that the highly polar pendant groups not react with the amine hydrogen so as not to cross-link the polymer. These relatively inert pendant groups include cyano, amido, acetyl and aryl. Typical chemical compounds which may be reacted with the polyalkylene imine include acrylonitrile, acrylamide, methacrylamide, N-alkyl acrylamides, methylmethacrylate, and styrenes. Preferred are acrylonitrile and methyl methacrylate.

The amount of pendant polar groups reacted onto the imine polymer should still leave at least 20 mole percent of the amine hydrogens still available for cross-linking for best results. Thus, the amount of polar pendant groups added to the composition ranges from 0 to about 80 mole percent of the alkylene imine equivalent weight of repeating unit, generally less than 20 mole percent. Particularly preferred is 0-10 weight percent.

Additional ingredients, added in minor quantities, may be included in the composition. These preferably include dyes, leveling agents, and colorants which are either soluble in the polymer or are dispersed in such small particle size so as not to introduce significant haze in the coating. Other typical ingredients which may be included are ultra-violet stabilizers, heat stabilizers and the like.

The method of application of the composition to the substrate is not critical to the invention. It may be applied by dip coating, spray coating or roller coating.

The coating composition prior to application may be prepared by any known method but best results are obtained when the solution is prepared by the scheme depicted in FIG. 7. In this method of providing fogging protection the polyalkylene imine is placed into solution, such as in water, alcohol, or water-alcohol mixtures (PAI solution). Water-lower alcohol mixtures are effective and mixtures containing 1 to 25% lower alcohols are preferred. 2-Propanol is most effective in the aqueous solution. If the optional adhesion promoters (polar reactant-PR) are to be reacted with the polyalkylene imine, it is preferred to add them to the solution before the addition of cross-linking compounds and allow them to react with the amine hydrogens (to form PAT-PR polymer -FIG. 7). Generally, as in the case of acrylonitrile, the reaction occurs spontaneously with the evolution of heat and it is only necessary to control the temperature to prevent exotherm runaway. The cross-linking chemical compounds (CL) are then added to the solution after which the substrate may be directly coated with the solution. For ease of handling, stability and best results it is preferred to allow or cause the cross-linking compound to react with the polyalkylene imine primarily as a chain extender (to form CL-PAI-PR polymer) such that it does not sufficiently cross-link the polymer to cause gel or precipitation of the polymer, preferably limiting reaction temperatures to the range of about 60.degree. to 90.degree.C for 1/4 to 1/2 hour. For these initial reactions the chain extension reaction is most easily carried out with low molecular weight polyalkylene imine and CL capable of reacting only with amine hydrogens. With the lower molecular polyimine the molecular weight of the extended polymer is more easily controlled to prevent gel. After the initial reaction with the cross-linking compound, the solution stabilizes and no further reaction takes place to gel or precipitate the polymer for a number of days. Refrigeration extends the life of the solution. After the substrate surface is coated with the solution, the coated surface (CL-PAI-PR polymer) may be immediately heated but it is preferred that most of the solvent be allowed to evaporate before heating. Temperatures to 130.degree.C, generally 60.degree. to 120.degree.C, preferably 70.degree.-90.degree.C, are used to fully cross-link the imine polymer (PAI-PR polymer crosslinked by CL). The lower the temperature and the shorter the time the better the color of the cured coating. A nitrogen atmosphere for curing also reduces color formation. Generally 15 to 60 minutes provides sufficient cure at the above temperature ranges. The hardness of the coating is controlled to a degree of the amount of heating.

For many substrates only cleaning prior to coating is necessary to provide good adhesion of the anti-fogging coating. However, when the substrate is particularly hydrophobic, it has been found effective to "etch" the surface before the coating is applied. In the case of glass the etching may be accomplished by dilute hydrofluoric acid. With polymeric substrates, such as polycarbonate, an acid wash, which tends to oxidize and/or sulfonate the surface, is particularly effective. A solution of 1 to 35% by weight chromic acid in concentrated sulfuric acid gives excellent results. For example, the treatment of polycarbonate appears to make the surface hydrophilic after only a few minutes exposure.

The degree of fogging protection provided by the coating is approximately proportional to the thickness of the coating. Good results are obtained when the coating is 0.5 to 3 mils or thicker, but for some uses thickness may range well outside these limits.

The following examples are provided for illustration and are not intended to limmit the scope of invention. All parts and percentages are by weight unless otherwise noted. The following abbreviations are used in the examples: ECH epichlorohydrin PEI (numbers) polyethylene imine (approximate number average molecular weight) EO ethylene oxide AN acrylonitrile MBA N, N'-methylene bisacrylamide GM glycidyl methacrylate G glycidol MMA methyl methacrylate S sytrene IPA isopropyl acrylamide

The following test procedures are used in the examples:

Qualitative determinations of resistance to fogging are made by breathing on the surface for at least ten seconds and observing whether water condenses on the surface. A plus (+) indicates that no significant condensation formed on the surface. A minus (-) indicates that condensation forms readily.

Quantitative determination as indicated by fogging time in seconds is determined by exposure of the surface to air at 40.degree.C saturated with water vapor. The sample is conditioned for 24 hours at 50 percent relative humidity, 25.degree.C. The water saturated air is passed through a 11/2 inch diameter tube at 1100 cc. per minute. At the end of the glass tube are 1/32 inch high projections so that the sample surface can be held against the end of the tube and still provide sufficient air flow across the surface. The fogging time is the time from the placement of the sample against the projections until fifty percent of the exposed circular area displays fogging.

As a bench-mark, uncoated polycarbonate fogs almost instaneously in this test to yield a value of one or two seconds. A commercial anti-fogging coating offered under the "HYDRON" trademark by Woodstream-Hydron Corporation of Lititz, Pennsylvania, believed to be described in Example I to IV of U.S. 3,488,215 to Shepherd et al, yields a fogging time of about 30 seconds.

Hardness is a qualitative measure of the thumbnail hardness and general abrasion resistance of the coating. A plus (+) indicates that the surface cannot be scratched with the finger nail and is generally abrasion resistant to handling and general use. A minus (-) indicates that the surface can be scratched and in most applications would be abraded easily. A plus/minus (+) indicates marginal results in some compositions. Pencil hardness commonly ranges from 2H to 4H.

Adhesion of the coating to the substrate is determined by scribing sets of horizontal and vertical lines 1/8 inch apart to yield a grid on the surface with a razor blade, applying a piece of pressure sensitive adhesive tape to the surface and quickly removing it. The quantitative measurement is the percent coating within the grid area lifted off.

The coated surface is immersed for sixteen hours in a 0.2% detergent solution at room temperature and wiped with a facial tissue. The surface quality is observed and in some instances adhesion tests are performed on the exposed samples.

A solution of an uncured embodiment of this invention is prepared by dissolving 13.6 part PEI(600) in 25 parts distilled water. A charge of 0.6 parts MBA is then dissolved in the solution followed by the gradual addition of 7.2 parts GM during which time the solution exotherms to about 60.degree.C. While maintaining the solution at about 60.degree.C, 4.0 parts ECH is added followed by the addition of 4.0 parts 2 -propanol. The solution is heated to 68.degree.C for 30 minutes and then immediately cooled to 25.degree.C over a period of 30 minutes. The solution is stable at ambient temperatures for at least 6 months.

The solution is dip-coated on substrates including polycarbonate, glass and a sheet of an interpolymer of allyl diglycol carbonate/vinyl acetate/methyl methacrylate and then cured for 30 to 60 minutes at 100.degree.C in a hot oven. The coatings are all resistant to fogging and yield 0% lift in the adhesion test after detergent solution soaking.

Example 1 is repeated except that the proportions and components are varied according to Table I. After cure for thirty minutes at 100.degree.C, the coatings have excellent adhesion to glass and polycarbonate substrates and have fogging times greater than 120 minutes after overnight equilibration at 50% relative humidity. The coatings are hard to the fingernail and yield 0% lift after detergent soak.

A lens from a safety goggle of commercially available polycarbonate resin in the shape pictured in FIG. 1 is washed in hot detergent solution, rinsed and dried, hot washed with trichloro-trifluoroethane and dried.

A coating formulation is prepared by dissolving 100 parts (2.3 equivalent weights) polyethylene imine (M.sub.n of 600; 500-2500 cps at 25.degree.C; at least 99% C.sub.2 H.sub.5 N) in ethylene glycol monoethyl ether/mixture of 1-and 2-propanol (1/1) at about 15% concentration. A charge of 55 parts AN (1 mole) is added to the solution and allowed to react. An exotherm of approximately 10.degree.C is observed. After the solution is allowed to cool to room temperature, 17 parts (0.1mole) MBA is added. The mixture may be heated to bring it into solution. After the solution is allowed to cool, 111 parts ECH (1.2 moles) are added. After the exotherm is dissipated the solution is heated to 85.degree.C. After cooling and filtering, the solution is clear and stable for more than 24 hours at 25.degree. and for at least a week at 0.degree.C.

The lens 2 is dipped into the solution, allowed to dry and cured in an oven at 90.degree.C for 15 to 60 minutes. The coating 3 is apparently fully cured at 30 minutes and significant yellowing does not occur until sixty minutes. The detergent stability of the coated goggle pictured in FIGS. 1 and 2 is good with fog times ranging from 50 to 65 seconds. After detergent exposure the fog time is 70 to 120 seconds with adhesion rated adequate.

The procedure of Example 7 is repeated except that the composition of the coating is as follows:

After the lens is dipped the coating is cured at 110.degree.C for 15 to 60 minutes. No appreciable improvement is observed by the longer cure times and the color intensity of the coating is increased upon exposure to the heat. The hardness is good and detergent stability excellent. The fog time ranges from 35 to 40 seconds with excellent adhesion indicated by 0% lift.

The above procedure is repeated except that the polycarbonate lens is "etched" by a procedure including the steps of a hot detergent wash, rinse, dry and a 30 second "etch" by 2% chromic acid in sulfuric acid at 25.degree.C. The lens is then rinsed, dried and dip coated with the composition above using the same procedure. The fog time is 40 to 50 seconds with excellent detergent stability. The adhesion remains excellent with 0% lift.

The procedure of Example 7 is repeated except that the PEI is reacted in a water solution of about 15 to 20% solids. The AN reaction yields a temperature rise of about 12.degree.C. The solution is heated to 75.degree.C after the ECH is added, and after filtering, a surfactant, nonyl phenyl polyethylene glycol ether, is added.

The lens is "etched" as in Example 8 and dipped in the coating solution. The coated lens is dried and cured for 15 to 60 minutes at 90.degree.C. The coatings are colorless and exhibit excellent detergent resistance. The fog time is 25 to 30 seconds and adhesion is 0% lift. When the etching of the lens is skipped, the surface was slightly mottled suggesting poor wetting by the coating solution.

The procedure of Example 7 is repeated except that the cmposition of the coating comprises PEI of various molecular weights and a single cross-linker in various proportions. Typical results are provided in Table II:

The procedure of Example 7 is repeated except that the composition of the coating is varied as shown in Table III. Typical results for coating compositions using combinations of various cross-linking compounds with and without other reactive groups on the PEI are provided. The data in Table III further illustrates that the mole concentration of reactive groups of the cross-linker may be a good deal higher than the number of amine-hydrogen sites on the PEI and still yield a useful coating.

Solutions of various reactants are prepared in concentrations of 10 to 50 parts per PEI (75,000) in 2-propanol. Polycarbonate lenses are dip coated in the solution after which the coating is cured to provide a thickness of 0.5 to 3 mils. Qualitative observations are provided in Table IV.

PEI (75,000) is a viscous liquid with a Brookfield viscosity of 15,000 to 25,000 cps. at 25.degree.C. While this uncross-linked imine polymer can be solution-coated on polycarbonate it is not permanent and only superficial anti-fogging characteristics are obtained. When compounds such as acrylonitrile are reacted onto the polymer, some improvement in the physical characteristics of the film is observed, however, the permanence of the coating is still poor. In general, the more hydrophobic the cross-linker is, the poorer the initial anti-fog characteristics. Thus, a compound such as divinyl benzene would generally be used in combination with other cross-linking compounds. Particularly effective are epichlorohydrin, glycidol, glycidyl methacrylate, bisphenol-A, fumaric acid, dichloromaleic anhydride, and benzaldehyde. Where both a plus and minus sign are shown under a physical property heading, it is an indication that marginal characteristics are obtained depending upon the substrate, concentration of the cross-linker, the molecular weight of the PEI and the conditions of the coating.

A solution of 100 parts PEI in 500 parts water is prepared. A charge of 55 parts acrylonitrile is added and allowed to react with the attendant temperature increase. While the solution is still warm, 16 parts methylene bisacrylamide is added after which the solution is cooled to 22.degree.C. An amount of 110 parts epichlorohydrin is added incrementally over a period of 1/2 hour to control the temperature rise. After the entire amount is added the solution is heated to 80.degree.C., then immediately cooled to 22.degree.C and filtered. The viscosity of the coating solution may be increased by reacting at 80.degree.C for 15 to 60 minutes. The solution is stable.

An abrasion resistant sheet of an interpolymer of allyl diglycol carbonate/vinyl acetate/methyl methacrylate is etched with chromic acid for 90 seconds at 22.degree.C. The sheet is dipped in the coating solution prepared as above, dried and cured at 90.degree.C in air for 1 hour. The fog time is 20 seconds and the adhesion is excellent in that there is 0% lift in the tape tests both before and after immersion in detergent solution for 16 hours.

The procedure of Example 7 is repeated except that the 100 parts PEI(600) is placed in solution in a mixture of water/2-propanol (8/1) before reaction with the other components. A polycarbonate lens is etched with chromic acid, rinsed, dried, and dipped into the solution. After drying the coated lens is cured at 90.degree.C for 15-60 minutes in nitrogen atmosphere. A hard, colorless coating is obtained with excellent detergent stability. At all cure times the adhesion is excellent.

The average coating weight on the lens is 0.23 grams per lens such that a coating of approximately one mil is obtained. The equilibrium absorption of the coating at 50% relative humidity is about 15%. At 80% relative humidity the equilibrium water absorption is about 25 to 45%. At 100% relative humidity the water absorption of the coating is almost 50% without effecting the adhesion of the coating or its utility as on anti-fog coating.

After the coating is allowed to reach equilibrium at 50% relative humidity and 22.degree.C, the fog tim ranges from 50 to 70 seconds depending on the cure time. After the part is immersed in detergent solution at 22.degree.C for 16 hours and air dried for 1/2 hour at 22.degree.C, the fog time is 95 to greater than 120 seconds. Even after the lens is brought to equilibrium at 80% relative humidity and 22.degree.C, the fogging time is still in the range of 30 to 45 seconds. The coating is unaffected after 16 hours at -6.degree.C and -78.degree.C.

Plate glass with mirror surface quality in the shape of FIG. 3 is spray coated with the composition of Example 7. After cure at 90.degree.C. for 30 minutes, a durable, fog-resistant mirror 5 is obtained as pictured in FIGS. 3 and 4. The surface 6 is optically transparent and resistant to repeated washings without losing its anti-fogging property.

A lens molded of polymethyl methacrylate of a molecular weight of about 100,000 in the shape of FIG. 5 is dip coated in the solution as prepared under Example 7. After the coating 15 is dried and cured for 30 minutes at 90.degree.C, an abrasion resistant, anti-fogging lens as pictured in FIGS. 5 and 6 is obtained.

A 20% solution of poly(2 methyl aziridine) with a molecular weight of 600 to 1,000, is prepared in water/2-propanol (4:1 by volume). This solution is reacted with 45 parts of acrylonitrile. While the solution is still warm, 16 parts MBA are added after which the solution is cooled to 22.degree.C. A charge of 110 parts ECH is added incrementally over a period of 1/2 hour to control the temperature rise. After this addition, the solution is held at 80.degree.C. for 15 to 30 minutes to increase viscosity to the range suitable for dipping or spraying application. After curing a good anti-fog coating is obtained.

The procedure of Example 14 is repeated except that the following components are used in the coating:

3.6 parts triethylene tetramine (0.084 mole)

2.0 parts AN (p.04 mole)

0.6 part MBA (0.004 mole)

4.0 parts ECH (0.043 mole)

After cure of the coating on either polycarbonate or the interpolymer substrate used in Example 13 for 40 minutes at 90.degree.C in air, the fog times are greater than 120 seconds and the surface is slightly soft.