HK1173166B - Methods for producing photosensitive microparticles, non-aqueous dispersions thereof and articles prepared therewith - Google Patents

Description

Method of making photosensitive microparticles, non-aqueous nanodispersions thereof, and articles made therefrom

Cross Reference to Related Applications

This application is a continuation-in-part application of U.S. patent application No. 10/892919 filed on 16.7.2004, which is hereby incorporated by reference in its entirety.

Technical Field

The present invention relates to non-aqueous nanodispersions of photosensitive polymeric microparticles. The invention also relates to a process for preparing the non-aqueous nanodispersions, curable film-forming compositions comprising them, and photosensitive coated substrates.

Photosensitive materials exhibit a response to electromagnetic radiation, including infrared, visible and ultraviolet radiation, as well as light amplification or laser light that excites emission. This response may be of the type where visible radiation is emitted by photosensitive materials upon exposure, such as fluorescent and phosphorescent materials; in which the wavelength of electromagnetic radiation passing through the material is varied, such as nonlinear optical materials; or in which there is a reversible color change, such as a photochromic material.

Aqueous dispersions of photosensitive microparticles, and aqueous film-forming compositions containing them, can have some disadvantages. For example, aqueous film-forming compositions tend to generate foam during formulation, much more so than solvent-based compositions. Foaming can make application difficult. The application of aqueous film-forming compositions often requires expensive humidity control equipment, as relative humidity affects the flow properties and drying rate of the coating. The choice of organic co-solvents is limited in aqueous compositions due to the evaporation rate and poor compatibility with aqueous media. Furthermore, the high surface tension of water makes certain substrates difficult to wet. Production equipment and lines that come into contact with the aqueous composition need to be corrosion resistant. This usually involves the use of plastic or expensive stainless steel in the production situation. Aqueous compositions are difficult to maintain acid free due to the stabilization mechanism of the acid in water. In aqueous coatings, the use of materials having water-sensitive functional groups, such as epoxy groups, is problematic because appearance problems such as haze in wet conditions can occur. Growth of microorganisms is also a problem in aqueous compositions.

Some products take advantage of the phenomena exhibited by photosensitive materials, such as optical elements such as optical memory elements and display elements. While products incorporating aqueous core/shell microparticles that exhibit photosensitive properties are known, it would be desirable to provide non-aqueous products in which the properties of the photosensitive material in the microparticles can be readily controlled so that the disadvantages of aqueous compositions can be avoided. It is also desirable that certain physical properties of the final product, such as hardness or abrasion resistance, can be controlled without adversely affecting the properties of the photosensitive material used in the product.

Detailed description of the invention

As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless expressly and unequivocally limited to one referent.

For the purposes of this specification, unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and other parameters used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

All numerical ranges herein include all numbers and ranges of all numbers in the recited numerical range. Notwithstanding that the numerical ranges and parameters setting forth the broadest scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

The various embodiments and examples of the invention set forth herein are intended to be non-limiting with respect to the scope of the invention.

The term "monomer" includes both a single monomer unit and oligomers comprising several monomer units.

The term "actinic radiation" includes light having a wavelength of electromagnetic radiation ranging from the ultraviolet ("UV") light range, through the visible light range, and further through the infrared range. Actinic radiation that may be used to cure the coating compositions used in the present invention typically has a wavelength of 150-2,000 nanometers (nm), 180-1,000nm, or 200-500 nm. Ultraviolet radiation in the wavelength range of 10-390nm may also be used. Examples of suitable ultraviolet light sources include mercury arc lamps, carbon arc lamps, low, medium or high pressure mercury lamps, vortex plasma arc lamps, and ultraviolet light emitting diodes. Suitable ultraviolet light-emitting lamps may include, but are not limited to, medium pressure mercury vapor lamps having an output of 200 and 600 watts/inch (79-237 watts/cm) over the length of the lamp tube.

According to the present invention there is provided a non-aqueous dispersion of photopolymer microparticles comprising: a) an organic continuous phase comprising an organic solvent; and b) photosensitive polymeric microparticles dispersed in the organic continuous phase, wherein the microparticles comprise an at least partially polymerized component having an integrated surface region and an interior region, wherein the surface region comprises a polymeric material that is soluble in the organic solvent, the interior region comprises a polymeric material that is insoluble in the organic solvent, and the surface region and/or interior region is photosensitive.

The organic solvent in the organic continuous phase is typically a polar solvent and may include, for example, one or more alcohols, such as mono-alcohols or glycols, including glycols, ethers, amides, nitriles, esters, ketones, and/or lactams. Polar solvents are defined as molecules having a non-uniform distribution of charge such that one end of each molecule is more positive than the other, making solutes dissolved therein susceptible to ion formation. Examples of particularly suitable solvents may include N-butanol, isobutanol, isopropanol, benzyl alcohol, ethylene glycol, propylene glycol, tetrahydrofurfuryl alcohol, propylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monobutyl ether, diethylene glycol butyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, dimethylformamide, N-methylpyrrolidone, methyl ethyl ketone, methyl amyl ketone, methyl ethyl ketone,a solvent (which is described as 2,2, 4-trimethyl-1, 1, 3-pentanediol monoisobutyl ester and is commercially available from Eastman Chemical Co.), and a mixture of the solvents. The use of organic solvents may assist in the formation of the crosslinked polymer microparticles.

The photopolymer microparticles are dispersed in an organic continuous phase. The microparticles comprise an at least partially polymerized component having an integrated surface region and an interior region. One or both of the surface region and the interior region may be photosensitive. The surface region comprises a polymeric material that is soluble in an organic solvent, and the interior region comprises a polymeric material that is insoluble in the organic solvent.

The non-aqueous nanodispersions of the present invention can be prepared in any of a variety of ways. For example, the non-aqueous dispersion may be prepared as follows:

a) preparing an aqueous dispersion of a photosensitive material and a polymerizable component, wherein the polymerizable component comprises at least one hydrophilic functional group and at least one hydrophobic functional group;

b) subjecting the dispersion of a) to conditions sufficient to form microparticles, such as high shear stress conditions;

c) at least partially polymerizing the polymerizable component;

d) combining the dispersion with an organic continuous phase comprising an organic solvent, typically a polar solvent; and

e) water is removed from the dispersion such that the final water content of the non-aqueous dispersion is less than 30 weight percent. It should be noted that e) can be performed before or after d).

The non-aqueous nanodispersions of the present invention may comprise water in an amount less than 30 wt.%.

The polymerizable component in the aqueous dispersion prepared in step a) may comprise at least one substantially hydrophilic monomer and at least one substantially hydrophobic monomer, the hydrophilic monomer and the hydrophobic monomer being capable of at least partially forming microparticles with the polymerizable component associated with a photosensitive material, such as a photochromic material. Alternatively, the aqueous dispersion may comprise an effective amount of at least one photosensitive material, the at least one polymerizable component comprising at least one hydrophilic functional group and at least one hydrophobic functional group. The photosensitive material and polymerizable component are capable of forming at least partially crosslinked photosensitive polymeric microparticles. The polymerizable component can further comprise at least one substantially hydrophilic prepolymer, at least one substantially hydrophobic prepolymer, and an effective amount of at least one organic photochromic material comprising at least one polymerizable group, the polymerizable component being capable of forming at least partially crosslinked photochromic polymeric microparticles.

The polymerizable component may further comprise a material copolymerizable with at least one of the substantially hydrophilic and substantially hydrophobic monomers, the material being hereinafter referred to as "copolymerizable material". In addition, the polymerizable component can have functionality that can react with the crosslinking material, be compatible with the host material, and have properties associated with the photopolymer microparticles described herein.

The phrase "microparticle capable of at least partially forming a polymerizable component associated with a photosensitive material" refers to a polymerizable component suitable for self-assembly into an at least partially formed microparticle. The self-assembly of the microparticles is due to the inclusion of the polymerizable component due to the difference in hydrophilicity and hydrophobicity between the hydrophilic functional group of the substantially hydrophilic monomer comprising the polymerizable component and the hydrophobic functional group of the substantially hydrophobic monomer comprising the polymerizable component. The photosensitive material may be associated with the microparticles by selecting a hydrophilic photosensitive material, a hydrophobic photosensitive material, or a photosensitive material having other properties that cause the photosensitive material to be chemically or physically associated with the resulting microparticles or polymerizable components.

After the microparticles are formed, the microparticles are typically polymerized. The phrase "at least partially polymerize and form at least partially crosslinked polymeric microparticles" refers to some to all of the monomers or prepolymers in the polymerizable component reacting and combining to form chain-like polymeric materials, and some to all of the reactive groups on these chain-like polymeric materials reacting and crosslinking to form a polymeric network, with some to all of the chains interconnected. The aforementioned reactive groups are chemical groups capable of undergoing polymerization reactions known to those skilled in the art. Examples of such polymerizable groups include methacryloxy, acryloxy, vinyl, allyl, carboxyl, amino, mercapto, epoxy, hydroxyl, and isocyanate groups.

The polymeric microparticles formed in steps b) and c) generally have a core/shell structure which makes them particularly suitable for use in the preparation of the non-aqueous nanodispersions of the present invention, in particular, polar non-aqueous nanodispersions. The core (i.e., interior region) and shell (i.e., the surface region) polymers are covalently linked or associated with each other. Otherwise, the compatibility of the shell polymer with the solvent in the organic continuous phase may cause the shell to dissolve away from the core material. Furthermore, the core is crosslinked and/or comprises a material that is not itself soluble in the organic continuous phase, and the shell comprises a polymer that is completely soluble in the organic continuous phase if it is not attached to the insoluble core. The solubility of the shell polymer renders the core/shell microparticles compatible with the solvent, while the insolubility of the core maintains the integrity of the microparticles by preventing the microparticles from completely dissolving in the solvent.

When the dispersion is combined with the organic continuous phase in step d), the dispersion may be poured into the organic continuous phase or the reverse operation is carried out. The water is removed from the dispersion using known methods, such as by ultrafiltration, distillation under reduced pressure or by centrifugation.

A further method of preparing a non-aqueous dispersion of photosensitive microparticles according to the present invention comprises:

a) preparing an aqueous dispersion of a substantially hydrophilic prepolymer component;

b) preparing an aqueous dispersion of a substantially hydrophobic prepolymer component, wherein the dispersion of a) and/or b) further comprises a photosensitive material;

c) combining the dispersions of a) and b) to form a mixture and subjecting the mixture to conditions sufficient to form microparticles;

d) polymerizing the prepolymer component of the mixture;

e) combining the mixture with an organic continuous phase comprising an organic solvent, typically a polar solvent; and

f) water is removed from the mixture such that the final water content of the non-aqueous dispersion is less than 30 wt.%. It should be noted that f) can be performed before or after e).

Adjuvant materials may also be incorporated into the non-aqueous dispersion, for example, conventional ingredients that aid in processing the polymerizable component or impart desired characteristics to the resulting microparticles. Examples of such ingredients include rheology control agents, surfactants, initiators, catalysts, cure inhibitors, reducing agents, acids, bases, preservatives, crosslinking materials, free radical donors, free radical scavengers, stabilizers such as ultraviolet light and thermal stabilizers, and adhesion promoters such as organofunctional silanes, siloxanes, titanates and zirconates, such adjuvant materials being known to those skilled in the art.

The non-aqueous nanodispersions of the present invention optionally may comprise other colorants such as nanopigments, and/or non-sensitizing dyes. Such colorants are particularly useful in the preparation of so-called "dark-to-darker" coating compositions. The term "nanopigment" refers to a pigment having an average primary particle size of up to 100 nm.

As previously mentioned, the aqueous dispersion used to prepare the non-aqueous nanodispersions of the present invention may comprise at least one polymerizable component comprising at least one substantially hydrophilic monomer and at least one substantially hydrophobic monomer. As used herein, the terms "substantially hydrophilic monomer" and "substantially hydrophobic monomer" refer to the relative hydrophilic or hydrophobic character of the monomers as compared to one another. The substantially hydrophilic monomer capable of polymerizing the component is more hydrophilic than the substantially hydrophobic monomer. Accordingly, the substantially hydrophobic monomers of the polymerizable component are more hydrophobic than the substantially hydrophilic monomers. One method of determining the hydrophilic/hydrophobic properties of a material is the well-known hydrophilic-lipophilic balance (HLB) number. The HLB number typically ranges from 1 to 20, with 1 being an oil-soluble material and 20 being a water-soluble material. With such a system, a substantially hydrophobic material as described herein would exhibit an HLB of less than 10, while a substantially hydrophilic material as described herein would exhibit an HLB of greater than 10.

The ratio of substantially hydrophilic monomers to substantially hydrophobic monomers may vary widely. The weight% of the substantially hydrophilic monomer and the substantially hydrophobic monomer in the polymerizable component can each range from 2 to 98 weight% based on 100% total polymerizable component solids. Examples of the ratio of substantially hydrophilic monomers to substantially hydrophobic monomers may be, but are not limited to, 20: 80 and 50: 50.

in certain embodiments, the substantially hydrophilic monomer is substantially compatible with water, has an affinity for water, and/or is capable of being at least partially dissolved in water using conventional mixing means. The substantially hydrophilic monomer used in the polymerizable monomer component of the present invention may include any hydrophilic monomer known to those skilled in the art. Examples of such hydrophilic monomers include monomers comprising the following hydrophilic functional groups, such as: acid functional groups; a hydroxyl functional group; a nitrile functional group; an amino functional group; an amide functional group; a carbamate functional group; ionic functional groups such as quaternary ammonium or sulfonium groups; or mixtures of said functional groups.

The degree of hydrophilicity and hydrophobicity of the monomers used to prepare the polymerizable components can vary, as known to those skilled in the art. The substantially hydrophobic monomers of the polymerizable component can be converted to substantially hydrophilic monomers. For example, the isocyanate groups on the hydrophobic monomers of the polymerizable component may be functionalized with siloxane groups by reacting the isocyanate groups with an organofunctional silane, such as aminopropyltriethoxysilane. After dispersion in water, the hydrolysable groups, such as alkoxysilanes, are at least partially hydrolysed to form hydrophilic silanol groups. These hydrophilic groups can be switched back to hydrophobic groups if they are able to react with the alcohol or themselves. The same functionalization process can be performed with available isocyanate groups on the polymerized and crosslinked photopolymer microparticles.

Examples of organofunctional silanes suitable for such hydrophobic to hydrophilic conversion processes may include, but are not limited to, 4-aminobutyltriethoxysilane, carboxymethyltriethoxysilane, isocyanatopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, mercaptomethylmethyl-diethoxysilane, or mixtures thereof.

Examples of the hydrophilic acid functional group-containing monomer may include, but are not limited to, acrylic acid, methacrylic acid, β -carboxyethyl acrylate, acryloxypropionic acid, 2-acrylamidomethylpropanesulfonic acid, 3-sulfopropyl acrylate, crotonic acid, dimethylolpropionic acid, fumaric acid, mono (C) of fumaric acid₁-C₈) Alkyl esters, maleic acid, mono (C) of maleic acid₁-C₈) Alkyl esters, itaconic acid, mono (C) of itaconic acid₁-C₈) Alkyl esters and mixtures thereof.

Examples of hydrophilic hydroxyl functional group-containing monomers may include, but are not limited to, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, poly (ethylene glycol) methacrylate, hydroxypropyl acrylate, hydroxybutyl methacrylate, hydroxybutyl acrylate, hydroxymethylethyl acrylate, hydroxymethylpropyl acrylate, dihexanolide acrylate, diethanolamine, dimethanolamine, or mixtures thereof. Examples of monomers containing nitrile functional groups include methacrylonitrile and acrylonitrile.

Examples of the hydrophilic amino functional group-containing monomer may include, but are not limited to, allylamine, dimethylallylamine, 2- (dimethylamino) ethyl methacrylate, 2- (tert-butylamino) ethyl methacrylate, 4-aminostyrene, dimethylaminoethyl vinyl ether, and N- (3-dimethylaminopropyl) methacrylamide.

Examples of suitable hydrophilic ionic functional group-containing monomers may include, but are not limited to, allyltrimethylammonium chloride, 2-trimethylammonium ethyl acryloyl chloride, and vinylbenzyldimethylsulfonium chloride.

Examples of the hydrophilic amide functional group-containing monomer may include, but are not limited to, methacrylamide and acrylamide.

Examples of hydrophilic carbamate functional group-containing monomers may include, but are not limited to, allyl carbamate, vinyl carbamate, the reaction product of hydroxyethyl carbamate and methacrylic anhydride, and the reaction product of hydroxyethyl carbamate and isophorone diisocyanate and hydroxyethyl acrylate.

Examples of hydrophilic vinyl functional group-containing monomers may include, but are not limited to, vinyl acetate, vinyl pyrrolidone, and vinyl propionate.

In certain embodiments of the present invention, hydrophobic monomers may include monomers that are substantially free of hydrophilic functionality and are substantially incompatible with water, have a lower affinity for water, and/or are only slightly soluble in water using conventional mixing means. The hydrophobic monomer used in the polymerizable component may include any hydrophobic monomer known to those skilled in the art. Examples of the hydrophobic functional group may include, but are not limited to, hydrocarbons having 4 or more carbon atoms. Further non-limiting examples of such functional groups are included in the description of hydrophobic monomers below.

Non-limiting examples of hydrophobic monomers can include free-radically polymerizable monomers including, but not limited to, vinyl aromatic monomers such as styrene, alpha-methylstyrene, tert-butylstyrene, and vinyltoluene; halogenated vinyl and vinylidene halides, such as vinyl chloride and vinylidene chloride; vinyl esters; vinyl ethers, vinyl butyrate, alkyl esters of acrylic and methacrylic acid having 4 to 17 carbon atoms in the alkyl group, including butyl methacrylate, butyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, 4-tert-butylcyclohexyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, butyl hexyl methacrylate, butyl hexyl acrylate, isooctyl methacrylate, isooctyl acrylate, isodecyl methacrylate, isodecyl acrylate, norbornyl methacrylate, norbornyl acrylate, lauryl methacrylate, and lauryl acrylate; and mixtures thereof.

Other suitable hydrophobic monomers may include, for example, organofunctional silanes having substantially non-hydrolyzable substituents such as alkoxy groups having 3 or more carbon atoms.

In certain embodiments, the polymerizable component comprises at least one copolymerizable material different from the at least one substantially hydrophilic monomer and the at least one substantially hydrophobic monomer. The copolymerizable material may be reacted with the substantially hydrophilic monomer to form a substantially hydrophilic prepolymer and/or reacted with the substantially hydrophobic monomer to form a substantially hydrophobic prepolymer.

The copolymerizable material may be any material that is copolymerizable with at least one of the substantially hydrophilic monomer and the substantially hydrophobic monomer. For example, the copolymerizable material may be a structural skeleton-forming material. Suitable copolymerizable materials may be selected from: an ethylenically unsaturated group-containing material; isocyanate-containing materials known to those skilled in the art, such as the reaction product of an isocyanate and other corresponding reactive materials, such as a polyol, wherein the reaction product has at least one reactive isocyanate group; hydroxyl-containing monomers known to those skilled in the art; epoxy-containing monomers known to those skilled in the art; carboxyl group-containing monomers known to those skilled in the art; ester group-containing monomers known to those skilled in the art, such as the reaction product of a polyol containing at least one carbonate group and a vinyl monomer, and the reaction product of a polyol containing at least one carbonate group and an isocyanate containing one reactive isocyanate group and at least one polymerizable double bond, are described in U.S. patent application publication No. US2003/0136948 (now U.S. Pat. No. 6,998,072) paragraphs [0041] - [0065], the disclosures of which are incorporated herein by reference; or a mixture of said copolymerizable materials.

The copolymerizable material may also include a silyl-containing material, such as an organofunctional silane having at least one polymerizable group, such as the organofunctional silanes previously described.

Non-limiting examples of suitable copolymerizable materials, such as ethylenically unsaturated group-containing monomers, may include vinyl monomers and ethylenically unsaturated monomers having functional groups selected from hydroxyl, carboxyl, amino, mercapto, (meth) acryloxy groups, such as methacryloxy or acryloxy groups, isocyanate groups, or mixtures thereof, as are known to those skilled in the art. The copolymerizable material may have more than two of the same polymerizable groups or more than two different polymerizable groups. Typically, the copolymerizable material is selected from (meth) acrylic monomers having at least one functional group selected from hydroxyl, amino, mercapto or mixtures thereof.

When necessary, the substantially hydrophilic monomers and/or the substantially hydrophobic monomers used to form the polymerizable component are selected based on the properties provided by the glass transition temperature of the respective polymer upon polymerization, as known to those skilled in the art. For example, monomers that form polymers with glass transition temperatures above room temperature, e.g., 23 ℃, tend to form stronger or stiffer polymers, while monomers that form polymers with glass transition temperatures below room temperature tend to be softer and more flexible. The nature of the monomer used to form the condition of the polymer microparticles can affect the performance of the photosensitive material. For example, in the case of organic photochromic materials that exhibit activated and non-activated states depending on the change in configuration, the soft and flexible conditions allow more freedom of movement and may result in improved performance, or the stronger and stiffer conditions allow less freedom of movement and may result in reduced performance. Formulating the polymerizable component with a material having properties that can affect the properties of the photosensitive material can provide the resulting photosensitive polymeric microparticles with conditions in which the properties of the photosensitive material can be controlled independently of the conditions surrounding the photosensitive polymeric microparticles. For example, the photopolymer microparticles may themselves be soft and flexible, but surrounded by or embedded in a strong and hard matrix or environment.

After polymerization, the substantially hydrophilic monomers and the substantially hydrophobic monomers each form a polymer, the glass transition temperature of which can vary widely. The glass transition temperature of the polymer formed after polymerization of the substantially hydrophobic monomer may be greater than or equal to the glass transition temperature of the polymer formed after polymerization of the substantially hydrophilic monomer. Alternatively, the glass transition temperature of the polymer formed after polymerization of the substantially hydrophobic monomer may be less than or equal to the glass transition temperature of the polymer formed after polymerization of the substantially hydrophilic monomer.

The substantially hydrophobic monomer may be selected to form a polymer after polymerization having a glass transition temperature of less than 23 ℃, for example 22.9 ℃ to 100 ℃ or 22 ℃ to 90 ℃. Alternatively, the substantially hydrophilic monomer is selected to form a polymer after polymerization having a glass transition temperature equal to or greater than 23 ℃, e.g., 23 ℃ to 130 ℃ or 24 ℃ to 100 ℃.

The substantially hydrophilic monomer and/or the substantially hydrophobic monomer may be a polyurethane material adapted to form a substantially strong and/or substantially flexible segment. The principle of preparing polyurethane materials by selecting components such as isocyanates and polyols to form strong or flexible segments, thereby forming suitable types of segments, is known to those skilled in the art. See, for example, U.S. Pat. No. 6,187,444 for a discussion of hard and soft segments in column 3, line 49 to column 4, line 46, the disclosure of which is incorporated herein by reference. The rigid segments of the polyurethane material impart toughness to the resulting material in which it is used that is not easily bent and does not break. The flexible segments of the polyurethane material result in the material being flexible and capable of bending completely or changing from straight or shape without breaking. In certain embodiments of the invention, the substantially hydrophobic monomer is a polyurethane material, such as a polyurethane (meth) acrylate prepolymer, that is adapted to form a flexible segment, and the substantially hydrophilic monomer is a polyurethane material, such as a polyurethane (meth) acrylate prepolymer, that is adapted to form a rigid segment. Alternatively, the substantially hydrophobic monomer is a polyurethane material adapted to form a rigid segment, and the substantially hydrophilic monomer is a polyurethane material adapted to form a flexible segment.

The polyurethane materials of the present invention can be prepared with isocyanates and polyols, amines and/or thiols, which can vary widely. Suitable materials and methods are known to those skilled in the art of polyurethane preparation.

When polyurethane-forming components such as organic components having hydroxyl, mercapto and/or amino groups and isocyanate are combined to prepare the polyurethane material of the present invention, the relative amounts of the ingredients are typically expressed as the ratio of the available number of reactive isocyanate groups to the available number of reactive hydroxyl, mercapto and/or amino groups, for example NCO: an equivalent ratio of X, wherein X represents OH, SH, NH and/or NH₂. For example, when one NCO equivalent weight of the isocyanate component is reacted with one X equivalent weight of the hydroxyl, mercapto and/or amino group containing component, NCO is obtained: the X ratio is 1.0: 1.0. NCO of polyurethane material: the X equivalence ratio can vary widely. For example, NCO: the equivalence ratio of X may range from 0.3: 1.0-3.0: 1.0 and so ranges there between are encompassed. When the ratio is greater than 1.0: at 1.0, the excess isocyanate groups may be blocked and/or further reacted, for example with urea or an organofunctional silane, to form hydrophilic groups, as known to those skilled in the art.

Non-limiting examples of isocyanate components may include modified or unmodified isocyanates containing components having free, blocked (e.g., with a suitable blocking agent) or partially blocked isocyanates, as known to those skilled in the art, selected from: toluene-2, 4-diisocyanate; toluene-2, 6-diisocyanate; diphenylmethane-4, 4' -diisocyanate; diphenylmethane-2, 4' -diisocyanate; p-phenylene diisocyanate; a biphenyl diisocyanate; 3,3 '-dimethyl-4, 4' -diphenylene diisocyanate; tetramethylene-1, 4-diisocyanate; hexamethylene-1, 6-diisocyanate; 2,2, 4-trimethylhexane-1, 6-diisocyanate; lysine methyl ester diisocyanate; bis (isocyanatoethyl) fumarate; isophorone diisocyanate; ethylene diisocyanate; dodecane-1, 12-diisocyanate; cyclobutane-1, 3-diisocyanate; 2-heptyl-3, 4-bis (9-isocyanatononyl) -1-pentyl-cyclohexane; cyclohexane-1, 3-diisocyanate; cyclohexane-1, 4-diisocyanate; dicyclohexylmethane-4, 4-diisocyanate or methylenebis (4-cyclohexyl isocyanate); methylcyclohexyl diisocyanate; hexahydrotoluene-2, 4-diisocyanate; hexahydrotoluene-2, 6-diisocyanate; hexahydrophenylene-1, 3-diisocyanate; hexahydrophenylene-1, 4-diisocyanate; m-tetramethylxylene diisocyanate; p-tetramethylxylene diisocyanate; perhydrodiphenylmethane-2, 4' -diisocyanate; perhydrodiphenylmethane-4, 4' -diisocyanate or a mixture thereof. Triisocyanates such as the biuret of any suitable diisocyanate can be used including 1, 4-tetramethylene diisocyanate and 1, 6-hexamethylene diisocyanate. Also, the biuret of cycloaliphatic diisocyanates such as isophorone diisocyanate and 4,4' -methylene-bis (cyclohexyl isocyanate) can be used. Examples of suitable aralkyl diisocyanates from which biurets can be prepared are m-xylylene diisocyanate and α, α, α ', α' -tetramethyl m-xylylene diisocyanate. Other trifunctional isocyanates may also be used, for example, trimers of isophorone diisocyanate, triisocyanatononane, triphenylmethane triisocyanate, 1,3, 5-benzene triisocyanate, 2,4, 6-toluene triisocyanate, adducts of trimethylol and tetramethylxylene diisocyanate (sold under the trade name CYTHANE 3160 by CYTEC Industries), and DESMODUR RN 3300 and DESMODUR N3600, which are trimers of hexamethylene diisocyanate, available from Bayer Corporation.

When the substantially hydrophilic monomer is prepared from a triisocyanate (especially an isocyanurate), the non-aqueous nanodispersion-containing photosensitive microparticles prepared therefrom can be formulated into an aminoplast resin-containing coating, which can thereby exhibit improved adhesion to a substrate in boiling water as measured by haze, as compared to a similar coating prepared from non-aqueous nanodispersion-containing photosensitive microparticles prepared from a diisocyanate. Other advantages of triisocyanates include faster fade kinetics for photochromic microparticles prepared from triisocyanates as compared to similar photochromic microparticles prepared from diisocyanates. Moreover, substantially hydrophilic monomers prepared from triisocyanates tend to have better long-term stability than similar hydrophilic monomers prepared from diisocyanates.

When the polyurethane material is formed in the presence of a catalyst, the catalyst may be selected from: lewis bases, Lewis acids and insertion catalysts, as described in Ullmann's Encyclopedia of Industrial Chemistry, 5 th edition, 1992, volume A21, pages 673 and 674, the disclosure of which is hereby incorporated by reference.

Non-limiting examples of organic polyols useful in the present invention as polyurethane-forming components may include (a) polycarbonate polyols; (b) low molecular weight polyols, for example polyols having a weight average molecular weight of less than 500, such as aliphatic diols, for example, C2-C10 aliphatic diols, triols, polyhydric alcohols and alkoxylated low molecular weight polyols; (c) a polyester polyol; (d) a polyether polyol; (e) an amide-containing polyol; (f) polyacrylic polyols; (g) an epoxy-based polyol; (h) a polyhydroxy polyvinyl alcohol; (i) a polyurethane polyol; or (j) mixtures thereof. The foregoing polycarbonate polyols may be formed by methods known in the art, as disclosed, for example, in U.S. Pat. No. 5,143,997 at column 3, line 43 to column 6, line 25, and U.S. Pat. No. 5,527,879 at column 2, line 10 to column 3, line 48. For example, polycarbonates are generally obtained by reaction of alcohols or phenols with phosgene or by transesterification of alcohols or phenols with dialkyl or diaryl carbonates. In a particular embodiment of the invention, the polycarbonate-functional diols used are obtained from the reaction of diols, such as 1, 6-hexanediol, C, for example, with phosgene or dimethyl carbonate₂(ethylene glycol) -C₃₆Diols such as neopentyl glycol, butanediol, 1, 10-decanediol, butylethylpropanediol, 2-ethyl-1, 3-hexanediol, cyclohexanedimethanol, 2, 4-trimethylpentane-1, 3-diol, ester diol 204, and/orPolytetrahydrofuran (Mn 250). Mn is frequently used<2000 polycarbonate diols, e.g. Mn<1000 of a polycarbonate diol. The use of such polycarbonate-functional diols is particularly suitable when the non-aqueous nanodispersions are used to prepare solvent-borne coating compositions containing non-hydroxylic solvents (e.g., esters, ethers, aromatics, and/or ketones). Improved compatibility between the microparticles and the solvent is demonstrated by reduced particle aggregation.

Other polyols may also be prepared by methods known in the art, as described in U.S. Pat. No. 6,187,444 at column 7, line 25 to column 12, line 15. The disclosure of which is hereby incorporated by reference.

The organic polyols, such as diols, triols, and the like, used to prepare the polyurethane materials of the present invention can be used to form prepolymers or adducts with isocyanates. Furthermore, the substantially hydrophilic or substantially hydrophobic prepolymers may each be prepared from hydrophilic monomers such as dimethylolpropionic acid, or hydrophobic monomers such as C₈An aliphatic diol is reacted with the isocyanate-reactive groups of the prepolymer. The prepolymer may be a substantially hydrophilic or a substantially hydrophobic polyurethane (meth) acrylate prepolymer, such as a polyurethane acrylate prepolymer, a polyurethane methacrylate prepolymer, or a mixture thereof.

The non-aqueous nanodispersions of the present invention comprise an effective amount of at least one photosensitive material. The term "effective amount of photosensitive material" means that such amount of photosensitive material in the polymerizable component and the resulting photosensitive polymeric microparticles produces a response that is detectable by instrumental or visual observation when irradiated with a suitable wavelength of electromagnetic radiation, such as a change in the wavelength or amount of radiation emitted by the photosensitive material, a change in the wavelength of radiation that passes through the photosensitive material, or a change in the visible color of the photosensitive material. The term "photosensitive material" includes organic photosensitive materials, inorganic photosensitive materials or mixtures thereof, but excludes colorants such as pigments and fixed hueing dyes and conventional dichroic dyes, unless dichroic properties are associated with the photochromic materials as described below. The colorant can be included as an adjuvant component in the non-aqueous nanodispersion and curable film-forming composition of the present invention. In one example, the photosensitive material is selected from fluorescent dyes, phosphorescent dyes, nonlinear optical materials, photochromic materials, or mixtures thereof.

Optionally, the photosensitive material further comprises one or more polymerizable groups as previously described. Various methods for attaching polymerizable groups to photosensitive materials are known to those skilled in the art. See, for example, U.S. Pat. No. 6,113,814, column 8, line 42-column 22, line 7, the disclosure of which is incorporated herein by reference. Other methods that may be employed are those for attaching functional groups to non-photosensitive materials, such as the method of U.S. patent 5,919,846, column 2, line 35 to column 4, line 42. The photosensitive material may be a chain-like polymeric material at least partially bonded to the polymerizable component.

As known to those skilled in the art, fluorescent and phosphorescent dyes emit visible radiation when an atom or molecule passes from a higher to a lower electronic state. The two dyes differ in that luminescence from fluorescent dyes occurs faster after exposure to radiation than from phosphorescent dyes.

Fluorescent dyes known to those skilled in the art may be used as the photosensitive material in the present invention. See Haughland, R.P, (1996) Molecular Probes Handbook for fluorescent Probes and Research Chemicals 6 th edition. Examples of fluorescent dyes include anthracene, tetracene, pentacene, aniline, benzophenone, coumarin, fluorescein, perylene, and mixtures thereof.

Phosphorescent dyes known to those skilled in the art may be used as the photosensitive material in the present invention. Examples of phosphorescent dyes include: metal-ligand complexes such as tris (2-phenylpyridine) iridium [ ir (ppy)3 ]; 2,3,7,8,12,13,17, 18-octaethyl-21H, 23H-platinum porphyrin (II) [ PtOEP ] and organic dyes such as eosin (2',4',5',7' -tetrabromofluorescein), 2' -bipyridine and erythro-bright red (2',4',5',7' -tetraiodofluorescein).

Nonlinear optical materials (NLOs) can have a unique crystalline structure that is optically anisotropic with respect to electromagnetic radiation, but can also be amorphous, such as gallium arsenide, and polymers incorporating various chromophores such as disperse red 1[2873-52-8]4- (N-ethyl-N-2-hydroxyethyl) amino-4' -nitroazobenzene. The term "anisotropic" as used herein refers to a property having at least one value that differs when measured in at least one different direction. Thus, an "optically anisotropic material" is a material that differs in at least one optical property value when measured in at least one different direction. Based on the anisotropic properties of NLO materials, the ordering or orientation of materials is used to take advantage of the full advantage of the nonlinear properties of these materials, as known to those skilled in the art. Some NLO materials change the light passing through them according to orientation, temperature, wavelength of light, etc. An example of this property of NLO materials is that red light of a low wavelength enters the ammonium dihydrogen phosphate crystal, releases photons of accumulated higher energy, and exits as blue light of a higher wavelength. See D.Arivuoli "Fundamentals of nonlinear optical materials" PRAMANA-journal of physics Vol 57, Nos. 5&6Nov. & Dec.2001, pp.871-883, the disclosures of which are incorporated herein by reference.

NLO materials known to those skilled in the art can be used as the photosensitive material in the present invention. See, Nalwa, H.S. and Miyata, S, Editors, Nonlinear Optics of organic molecules and Polymers, CRC, 1997.

Examples of NLO materials other than the foregoing include: 4-dimethylamine-4-nitrostilbene; 4- [4- (phenylazo) -1-naphthylazo ] phenol; N-ethyl-N- (2-hydroxyethyl) -4- (4-nitrophenylazo) aniline; and (S) - (-) -1- (4-nitrophenyl) -2-pyrrolidinemethanol.

The photochromic material has at least two states, a first state having a first absorption spectrum and a second state having a second absorption spectrum different from the first absorption spectrum, and is switchable between the two states at least in response to at least two different wavelengths of actinic radiation. For example, isomer a of a photochromic material in a first absorption spectrum, e.g., the "clear" state, is exposed to light of a first wavelength and isomerizes to isomer B in a second absorption spectrum, e.g., the "colored" state, which discontinuously isomerizes back to isomer a upon exposure to light of a second and different wavelength or upon exposure to light of the first wavelength. Typically, photochromic materials in the transparent state are considered "unactivated" and in the colored state are considered "activated". Within the category of photochromic materials, there are thermally reversible and non-thermally reversible photochromic materials. Thermally reversible photochromic materials are capable of switching between first and second states in response to at least actinic radiation and returning to the first state in response to the removal of thermal energy, such as any form of heat, or activating radiation. Non-thermally reversible (or photo-reversible) photochromic materials are adapted to switch states in response to actinic radiation rather than thermal energy.

Both thermally reversible and non-thermally reversible photochromic materials may be adapted to exhibit photochromic and dichroic (e.g., at least partially linearly polarizing) properties under suitable conditions and are referred to as photochromic-dichroic materials. As used herein, "at least partially linearly polarized" refers to confining some or all of the vibrations of the electric field vector of the light wave to one direction or plane. As discussed in more detail below, photosensitive articles comprising optically anisotropic materials, such as nonlinear optical materials and/or photochromic-dichroic materials, can be at least partially oriented.

The photochromic material may include a variety of photochromic materials that may be used as the photosensitive material in the present invention. For example, the photochromic material may be selected from inorganic photochromic materials, organic photochromic materials, or mixtures thereof.

The inorganic photochromic material can include crystallites of silver halide, cadmium halide, and/or copper halide. Other inorganic photochromic materials can be prepared, for example, by adding europium (II) and/or cerium (III) to an inorganic glass such as sodium silicate glass. The inorganic photochromic material can be added to the molten glass and formed into particles, and then incorporated into the aqueous composition of the present invention to form microparticles comprising such microparticles. The glass microparticles may be formed by any of a variety of methods known in the art. Inorganic photochromic materials are further described in Kirk Othmer Encyclopedia of chemical technology 4 th edition, volume 6, page 322-325.

The photochromic material is typically at least one organic photochromic material comprising at least one active absorption maximum in the range of 300-1000 nanometers, as known to those skilled in the art. In certain embodiments, the organic photochromic material comprises a mixture of (a) at least one organic photochromic material having a visible lambda maximum of from 400 to less than 550 nanometers and (b) at least one organic photochromic material having a visible lambda maximum of 550-700 nanometers.

Photochromic materials may include the following classes of materials: pyrans, oxazines, fulgides, fulgimides, diarylethenes or mixtures thereof. The photochromic material can be a thermally reversible photochromic material and/or a non-thermally reversible photochromic material. For example, the photochromic material may be selected from thermoreversible pyrans, thermoreversible oxazines, thermoreversible fulgides, thermoreversible fulgimides or mixtures thereof. Furthermore, the photochromic material can be a non-thermally reversible fulgide, a non-thermally reversible fulgimide, a non-thermally reversible diarylethene, or a mixture thereof. The photochromic material can also be a photochromic-dichroic material.

Examples of photochromic pyrans that can be used in the present invention include benzopyrans, and naphthopyrans, such as naphtho [1,2-b ]]Pyran, naphtho [2,1-b ]]Pyrans, and indene-fused naphthopyrans, such as those disclosed in U.S. Pat. No. 5,645,767 at column 2, line 16 to column 12, line 57, and heterocycle-fused naphthopyrans, such as those disclosed in U.S. Pat. No. 5,723,072 at column 2, line 27 to column 15, line 55, 5,698,141 at column 2, line 11 to column 19, line 45, 6,153,126 at column 2, line 26 to column 8, line 60, and 6,022,497 at column 2, line 21 to column 11, line 46, the disclosures of which are incorporated herein by reference, and spiro-9-fluoreno [1,2-b ] and spiro-9-naphtho]Pyrans, phenanthropyrans, quinolinopyrans; fluoranthenopyrans and spiropyrans, for example spiro (benzindoline) naphthopyrans, spiro (indoline) benzopyrans, spiro (indoline) naphthopyrans, spiro (indoline) quinopyrans and spiro (indoline) pyrans. More specific example descriptions of naphthopyrans and complementary organic photochromic substancesIn U.S. patent 5,658,501, column 1, line 64-column 13, line 17, the disclosure of which is incorporated herein by reference. Spiro (indoline) pyrans are also described in textbooks,Techniques in Chemistryvolume III, "Photochromism", chapter 3, Glenn h.brown, Editor, John Wiley and sons, inc., New York, 1971, also incorporated herein by reference.

Examples of photochromic oxazines that may be used in conjunction with the various embodiments disclosed herein include benzoxazines, naphthoxazines, and spiro oxazines, such as spiro (indoline) naphthoxazines, spiro (indoline) pyridobenzoxazines, spiro (indoline) naphthoxazines, spiro (indoline) benzoxazines, spiro (indoline) fluoranthene oxazines, and spiro (indoline) quinoline oxazines.

Examples of thermally reversible photochromic fulgides or fulgimides that may be used in conjunction with the various embodiments disclosed herein include: fulgides and fulgimides, disclosed in U.S. Pat. No. 4,685,783 at column 1, line 57 to column 5, line 27, the disclosure of which is incorporated herein by reference, and mixtures of any of the foregoing photochromic materials/compounds.

When the photochromic material comprises at least two photochromic compounds, the photochromic compounds may be linked to each other through a linking group substituent on each photochromic compound. For example, the photochromic material can be a polymerizable photochromic compound or photochromic compound ("compatible photochromic material") that is compatible with the host material. Examples of polymerizable photochromic materials that can be used in conjunction with the various embodiments disclosed herein are disclosed in U.S. Pat. No. 6,113,814 at column 2, line 23 to column 23, line 29, the disclosure of which is incorporated herein by reference. Examples of compatible photochromic materials that can be used in the present invention are disclosed in U.S. Pat. No. 6,555,028 at column 2, line 40 to column 25, line 26, the disclosure of which is incorporated herein by reference. A substantially hydrophilic polymerizable photochromic material can be used as the substantially hydrophilic monomer in the polymerizable component. Alternatively, a substantially hydrophobic polymerizable photochromic material can be used as the substantially hydrophobic monomer in the polymerizable component.

Other suitable photochromic groups and complementary photochromic groups are described in U.S. patent 6,080,338, column 2, line 21-column 14, line 43; 6,136,968 column 2, line 43-column 20, line 67; 6,296,785 column 2, line 47-column 31, line 5; 6,348,604 column 3, line 26-column 17, line 15; 6,353,102 column 1, line 62-column 11, line 64; and 6,630,597, column 2, line 16-column 16, line 23. The disclosures of the foregoing patents are hereby incorporated by reference.

Still further suitable photochromic materials include photochromic-dichroic materials such as those disclosed in U.S. patent application publication 20050004361 (now U.S. patent 7,342,112) paragraphs [0024] - [00157], the disclosure of which is incorporated herein by reference. Such materials may be used to provide polarizing properties to the at least partially oriented microparticles described below. Examples of such photochromic-dichroic compounds include:

(1) 3-phenyl-3- (4- (4- (3-piperidin-4-yl-propyl) piperidino) phenyl) -13, 13-dimethyl-indeno [2',3':3,4] -naphtho [1,2-b ] pyran;

(2) 3-phenyl-3- (4- (4- (3- (1- (2-hydroxyethyl) piperidin-4-yl) propyl) piperidino) phenyl) -13, 13-dimethyl-indeno [2',3':3,4] naphtho [1,2-b ] pyran;

(3) 3-phenyl-3- (4- (4- (4-butyl-phenylcarbamoyl) -piperidin-1-yl) phenyl) -13, 13-dimethyl-6-methoxy-7- (4-phenyl-piperazin-1-yl) indeno [2',3':3,4] naphtho [1,2-b ] pyran;

(4) 3-phenyl-3- (4- ([1,4] -bipiperidinyl-1 ' -yl) phenyl) -13, 13-dimethyl-6-methoxy-7- ([1,4' ] bipiperidinyl-1 ' -yl) indeno [2',3':3,4] naphtho [1,2-b ] pyran;

(5) 3-phenyl-3- (4- (4-phenyl-piperazin-1-yl) phenyl) -13, 13-dimethyl-6-methoxy-7- (4- (4-hexylbenzoyloxy) -piperidin-1-yl) indeno [2',3':3,4] naphtho [1,2-b ] pyran; or

(6) Mixtures of said pyrans.

In addition to the aforementioned photochromic materials, examples of non-thermally reversible diarylethene photochromic materials are described in U.S. patent application 2003/0174560 paragraphs [0025] - [0086], and non-thermally reversible fulgides or fulgimides are described in U.S. patent 5,631,382 at column 2, line 35 to column 12, line 8, the disclosures of which are incorporated herein by reference.

In certain embodiments, the photosensitive material is a photochromic material comprising a pyran selected from the group consisting of:

(a)3, 3-bis (4-methoxyphenyl) -6,11, 13-trimethyl-13- (2- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2',3':3,4] naphtho [1,2-b ] pyran;

(b)3- (4-methoxyphenyl) -3- (4- (2-hydroxyethoxy) phenyl) -13, 13-dimethyl-3H, 13H-indeno [2',3':3,4] naphtho [1,2-b ] pyran;

(c)3- (4-methoxyphenyl) -3- (4- (2-hydroxyethoxy) phenyl) -6, 7-dimethoxy-11-trifluoromethyl-13, 13-dimethyl-3H, 13H-indeno [2',3':3,4] naphtho [1,2-b ] pyran;

(d)3, 3-bis (4-methoxyphenyl) -13, 13-dimethyl-3H, 13H-indeno [2',3':3,4] naphtho [1,2-b ] pyran;

(e)3- (4-methoxyphenyl) -3- (4- (2-hydroxyethoxy) phenyl) -6, 11-difluoro-13, 13-dimethyl-3H, 13H-indeno [2',3':3,4] naphtho [1,2-b ] pyran; or

(f) Mixtures of said pyrans.

Methods for preparing photochromic materials with or without at least one polymerizable group are known to those skilled in the art. For example, and without limitation, 3, 3-bis (4-methoxyphenyl) -6,11, 13-trimethyl-13- (2- (2- (2-hydroxyethoxy) ethoxy-3H, 13H-indeno [2',3':3,4] naphtho [1,2-b ] pyran (photochromic material a) can be prepared according to the method of example 8 of U.S. patent No. 6,113,814, which is incorporated herein by reference, except that in step 7 of the method, triethylene glycol is used in place of diethylene glycol.

Photochromic materials such as (b)3- (4- (2-hydroxyethoxy) phenyl) -3- (4-methoxyphenyl) -13, 13-dimethyl-3H, l 3H-indeno [2',3':3,4] naphtho [1,2-B ] pyran (photochromic material B) can be prepared by reacting 7, 7-dimethyl-5-hydroxy-7H-benzo [ C ] fluorene with 1- (4- (2-hydroxyethoxy) phenyl) -1- (4-methoxyphenyl) -2-propan-1-ol using methods known to those skilled in the art.

Photochromic materials such as (c)3- (4-methoxyphenyl) -3- (4- (2-hydroxyethoxy) phenyl) -6, 7-dimethoxy-11-trifluoromethyl-13, 13-dimethyl-3H, 13H-indeno [2',3':3,4] naphtho [1,2-b ] pyran (photochromic material C) can be prepared according to the method of example 1 of U.S. patent application publication 2008/0103301, except that 1- (4- (2-hydroxyethoxy) phenyl) -1- (4-methoxyphenyl) -2-propan-1-ol is used in place of 1, 1-bis (4-methoxyphenyl) -2-propan-1-ol in step 6, which example is incorporated herein by reference.

Photochromic materials such as (d)3, 3-bis (4-methoxyphenyl) -6, 11-dimethoxy-13-butyl-13- (2-hydroxyethoxy) -3H, 13H-indeno [2',3':3,4] naphtho [1,2-b ] pyran (photochromic material D) can be prepared using the same method as that used for the photochromic material a above, except that, 3, 3-bis (4-methoxyphenyl) -6, 11-dimethoxy-13-butyl-13-hydroxy-3H, 13H-indeno [2',3':3,4] naphtho [1,2-b ] pyran and ethylene glycol are reacted together in step 7 of example 8 of U.S. Pat. No. 6,113,814.

Photochromic materials such as (e)3- (4-methoxyphenyl) -3- (4- (2-hydroxyethoxy) phenyl) -6, 11-difluoro-13, 13-dimethyl-3H, 13H-indeno [2',3':3,4] naphtho [1,2-B ] pyran (photochromic material E) can be prepared according to the method in example 1 of U.S. Pat. No. 7,556,751B2, except that in step 5 1- (4- (2-hydroxyethoxy) phenyl) -1- (4-methoxyphenyl) -2-propan-1-ol is used instead of 1, 1-bis (4-methoxyphenyl) -2-propan-1-ol, which example is incorporated herein by reference.

Photochromic materials such as 3, 3-bis (4-methoxyphenyl) -6-methoxy-7-morpholinyl-13-ethyl-13- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2',3':3,4] naphtho [1,2-b ] pyrans can be prepared by reacting 2-morpholino-3-methoxy-5, 7-dihydroxy-7-ethyl-7H-benzo [ C ] fluorene (which can be prepared according to step 2 of example 9 of U.S. patent 6,296,785, which is incorporated herein by reference, using appropriate alternative starting materials) with 1, 1-bis (4-methoxyphenyl) -2-propan-1-ol (which can be prepared according to the method of example 1 of U.S. patent 5,458,814, step 1, which is incorporated herein by reference) using methods known to those skilled in the art.

Similarly, photochromic materials such as 3- (4-fluorophenyl) -3- (4-methoxyphenyl) -6, 7-dimethoxy-13-ethyl-13- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2',3':3,4] naphtho [1,2-b ] pyran can be prepared according to the method for photochromic material a except that 3- (4-fluorophenyl) -3- (4-methoxyphenyl) -6, 7-dimethoxy-13-ethyl-13-hydroxy-3H, 13H-indeno [2',3':3,4] naphtho [1,2-b ] pyran and diethylene glycol.

Photochromic materials such as 3, 3-bis (4-methoxyphenyl) -6,11, 13-trimethyl-13-hydroxy-3H, 13H-indeno [2',3':3,4] naphtho [1,2-b ] pyrans can be prepared according to the method of example 5 of U.S. Pat. No. 5,645,767, which is incorporated herein by reference.

The photosensitive materials described herein may be selected from a variety of materials. Examples include: a single photoactive compound; a mixture of photosensitive compounds; a material comprising at least one photosensitive compound, such as a polymer resin or an organic monomer solution; such materials as monomers or polymers chemically bound to at least one photosensitive compound; a photosensitive polymer such as a photochromic polymer comprising photochromic compounds bonded together; or mixtures thereof.

When the photosensitive material is an organic photochromic material comprising at least one polymerizable group and a copolymerizable material is present, the polymerizable component typically comprises from 2 to 25 weight percent of a substantially hydrophilic prepolymer, from 2 to 25 weight percent of a substantially hydrophobic prepolymer, from 1 to 45 weight percent of the photochromic material and from 5 to 95 weight percent of one or more copolymerizable monomers, based on the total weight of the polymerizable component solids taken as 100%. More specifically, the polymerizable component can comprise 10 to 25 weight percent of a substantially hydrophilic prepolymer, 10 to 25 weight percent of a substantially hydrophobic prepolymer, 5 to 15 weight percent of a photochromic material, and 35 to 75 weight percent of one or more copolymerizable monomers. Each of the components of the polymerizable component can range between the values of each of the ranges encompassed by the foregoing ranges. In certain embodiments, the organic photochromic is present in an amount up to 50 weight percent of the total solids weight of the polymerizable component.

Further examples of the present invention include at least partially crosslinked photopolymer microparticles comprising an at least partially polymerized component comprising an integral surface region and an interior region, wherein said surface region comprises at least one substantially hydrophilic region, said interior region comprises at least one substantially hydrophobic region, and at least one of said surface and/or interior regions is photosensitive. In some cases, the photosensitive surface and/or interior region comprises an effective amount of at least one photosensitive material selected from fluorescent materials, phosphorescent materials, nonlinear optical materials, photochromic materials, or mixtures thereof. Typically, the inner region is adapted to be light sensitive. The photosensitive material may be substantially non-extractable, in particular cases the photosensitive material is a photochromic material.

The at least partially crosslinked polymeric microparticles are formed by self-assembly and partial polymerization of a polymerizable component in an aqueous environment. During self-assembly of the microparticles, the substantially hydrophilic region is oriented to the exterior and forms the surface region, while the substantially hydrophobic region is oriented to the interior and forms the interior region. The term "surface region" as used herein refers to a continuous region outside the microparticle (shell) and "interior region" encompasses a continuous region inside the microparticle (core), all regions being integral.

The at least one photosensitive material is typically adapted to be substantially non-extractable. The non-extractable sensitive material is also typically a photochromic material. The photochromic material is typically an organic photochromic material and may be substituted with at least one polymerizable group. By substantially non-extractable is meant that microparticles of a substantially non-extractable photosensitive material release less photosensitive material than microparticles of the same photosensitive material that are substantially extractable, because no measures are taken to prevent extraction, such as providing the photosensitive material with at least one polymerizable group that is capable of reacting with a polymerizable component described below.

The relative extractability of photosensitive material from the photosensitive polymeric microparticles (exemplified by organic photochromic materials) can be tested by including an effective amount of photochromic polymeric microparticles of substantially non-extractable photochromic materials (such as photochromic a described above, having at least one polymerizable group capable of reacting with a polymerizable component) in one part of the film-forming coating composition used in the examples, and including an effective amount of photochromic polymeric microparticles of substantially extractable photochromic materials (such as photochromic F described above, having no polymerizable group capable of reacting with a polymerizable component) in another part of the coating composition. The term "effective amount" as used herein means that a sufficient amount of photochromic polymeric microparticles is used to produce a photochromic effect discernible to the naked eye upon activation. The coating composition containing each type of photochromic polymeric microparticle is applied as an at least partial coating to the lens and at least partially cured as described in the examples herein. The absorbance of the at least partially cured coated lens and an uncoated lens of the same material at a suitable wavelength, such as 390 nanometers (nm), is measured to measure the initial amount of photochromic material and the absorbance of the lens material, respectively. The absorbance of the uncoated lenses was subtracted from the absorbance of each coated lens to calculate the uv stabilizer typically present in the lens material. The coated lenses as well as the uncoated lenses are immersed in separate containers with an equal amount of at least partially soluble solvent for the photosensitive material, such as Tetrahydrofuran (THF), which is kept at 23 ℃, e.g. room temperature. At 30 minute intervals, the lenses were removed, dried and tested for their absorbance at 390nm, and the absorbance of the uncoated lens was subtracted from each of the at least partially coated lenses. This is continued until the absorbance reading of the coated lens no longer changes significantly, indicating that an extractable amount of photochromic material has been extracted.

With respect to the photopolymer microparticles of the present invention, the amount of substantially non-extractable photosensitive material released by the photopolymer microparticles changes unexpectedly from slightly less to significantly less than the extractable photosensitive material released by the photopolymer microparticles. In other words, less than 10% to less than 100% of photosensitive material can be released with substantially non-extractable photosensitive material as compared to the nanoparticulate particles with extractable photochromic material.

The photosensitive material can become substantially non-extractable by trapping because it is trapped within the resulting polymer network of the at least partially crosslinked polymer microparticles due to the size of the photosensitive material; for example, a particulate photosensitive material, such as glass particulates comprising an inorganic photochromic material, or a photochromic oligomer or photochromic polymer having a number average weight and/or configuration that can be trapped due to size. Alternatively, the photosensitive material may be at least partially bound to the polymer network by covalent bonds, for example, by at least one functional group reactive with the surface and/or interior region. The photosensitive material may also be locked in by including physical dimensions, hydrogen bonding, and covalent bonding.

It has been found that substantially non-extractable organic photosensitive materials, such as organic photochromic materials, remain in the physical phase to which they are added. For example, a substantially non-extractable organic photochromic material associated with a substantially hydrophobic region of an interior region tends not to migrate to the substantially hydrophilic region and crystallize of the surface region.

The size of the photopolymer microparticles of the present invention can vary widely. For example, the size of the microparticles of the present invention may range from 10 to 10,000 nanometers (nm) or from 20 to 5000nm or from 30 to 1500nm or from 40 to 1000nm or from 50 to 500nm or from 60 to 200nm in average particle size, e.g., volume average particle size, as determined by measuring the particle size with a laser diffraction particle sizer, assuming that each particle is spherical, the resulting "particle size" represents the diameter of the smallest sphere that completely surrounds the particle. The average particle size of the photopolymer microparticles ranges between any of the foregoing values, including the values recited, e.g., 40 to 120 nm.

When the average particle size of the photopolymer microparticles is below 50nm, the size can be determined by ultraviolet or X-ray-laser light scattering, atomic force microscopy, neutron scattering or other methods known to those skilled in the art. When the average particle size is greater than 50nm and up to 1000nm, the average particle size may be measured according to known visible light-laser scattering techniques or it may be determined by visually examining an electron micrograph of a transmission electron microscope ("TEM") image, in which the diameter of the particles in the image is measured, and calculating the average particle size based on the magnification of the TEM image. When the average particle size is greater than 1000nm, the size can be measured by using optical microscopy methods known to those skilled in the art.

The aforementioned photopolymer microparticles may comprise a functionality that can react with the crosslinking material. The functionality also enables the photopolymer microparticles to react with host material components, such as polymeric organic materials, to make the photopolymer microparticles more compatible with the host. The term "more compatible" means that the combination of the photopolymer microparticles and the host material exhibits a lower likelihood of haze or haze, which is a typical indication of lack of compatibility. In one embodiment of the invention, at least a portion of the functionality suitable for reaction is hydrophilic, e.g., hydroxyl and carboxyl functional groups. Examples of such functional groups include: hydroxyl, carboxyl, epoxy, carbamate, amino, mercapto, amide and/or urea groups.

With respect to the cross-linked material, the cross-linked material is typically selected from: a material comprising two or more reactive unsaturation sites; a material comprising two or more of the foregoing functional groups; a material comprising one or more reactive unsaturation sites and one or more of the foregoing functional groups; or mixtures of such cross-linked materials. Examples of crosslinked materials of hydroxyl, carboxyl, amide, and carbamate functional group-containing materials include aminoplast resins, phenolplast resins, or mixtures thereof. Aminoplast resinsExamples of (c) are available from CYTEC Industries, Inc. under the trademark CYMEL, for example327. 328, 345, 350, 370 and 385 and are available under the trademark RES IMENE from Monsanto Chemical Co.

Polyisocyanates and blocked polyisocyanates and polyethylenimines can be used as crosslinking materials for hydroxyl-and primary and/or secondary amino-containing materials. Examples of polyisocyanates and blocked isocyanates suitable for use as crosslinkers for the photosensitive microparticles of the present invention are those described in U.S. patent 4,546,045, column 5, lines 16-38; and those of U.S. patent 5,468,802, column 3, lines 48-60, the disclosures of which are incorporated herein by reference.

Examples of crosslinking materials for the hydroxyl and primary and/or secondary amino groups include anhydrides well known in the art. Examples of anhydrides suitable for use as crosslinking materials are those described in U.S. Pat. No. 4,798,746 column 10, lines 16-50; and those of U.S. patent 4,732,790, column 3, lines 41-57, the disclosures of which are incorporated herein by reference.

Examples of materials for the carboxyl functional group cross-linking include polyepoxides and carbodiimides such as those sold under the trademark CARBODILITE by Nisshinbo Industries Inc, japan.

Examples of crosslinking materials for epoxy-functional group-containing materials are polyacids, which are well known in the art. Examples of suitable polyacids for use as crosslinking materials are those described in U.S. patent 4,681,811, column 6, line 45 to column 9, line 54, the disclosure of which is incorporated herein by reference.

Examples of materials for carbonate and unblanked ester crosslinking include polyamines well known in the art. Examples of polyamines suitable for use as the crosslinking material for the photopolymer microparticles of the present invention are those described in U.S. Pat. No. 4,046,729 at column 6, line 61 to column 7, line 26, the disclosure of which is incorporated herein by reference.

Examples of crosslinking materials for hydroxyl functional group-containing materials include siloxanes,Silanes and/or their hydrolysates, which are hardcoat preparation coating fluorine solutions such as sold by PPG industries, IncTypical composition of the coating solution. Further examples include silyl-substituted materials such as tris [3 (trimethoxysilyl) propyl]Isocyanurates, as is well known in the art.

Mixtures of the foregoing crosslinking materials may be used as desired and appropriate.

In a series of further embodiments, reactivity with cross-linking materials and other physical properties, such as those described below, may be associated with the photopolymer microparticles of the present invention. The microparticles may be adapted to have these properties by adding a material that brings these properties during the formation of the polymerizable component and/or after the formation of the at least partially crosslinked photopolymer microparticles.

The photosensitive polymeric microparticles are made magnetic or magnetically responsive by the introduction of a magnetic material and/or a magnetically responsive metal oxide during and/or after the preparation of the microparticles. Examples of such materials include superparamagnetic metal oxides, paramagnetic metal oxides, ferromagnetic metal oxides, such as ferrites, or mixtures thereof, as known to those skilled in the art. Magnetic microparticles are available from Dynal Biotech or can be prepared using art-recognized methods, such as those disclosed in, for example, U.S. patent 4,358,388, column 1, line 42-column 7, line 39, and 5,356,713, column 1, line 47-column 5, line 12, the disclosures of which are incorporated herein by reference.

The photopolymer microparticles may be electrically conductive by adding an electrically conductive material to the photopolymer microparticles. Conductive fillers, such as carbon fillers, carbon black or metal fibers, can be added during and/or after the preparation of the microparticles. The amount of conductive material added can vary widely provided that the percolation threshold is met or exceeded, e.g., the filler concentration at which the microparticles will conduct current, and the conductive polymer can also be added to the microparticles by including monomers of such polymers in the polymerizable component. Examples of the conductive polymer include: polyaniline-based polymers, polypyrrole-based polymers, polythiophene-based polymers, polyethylene oxide-based polymers, or copolymers thereof. The preparation and use of the electrically conductive material can be accomplished using techniques known to those skilled in the art. See Kirk Othmer Encyclopedia of Chemical Technology 4 th edition, volume 9, "conductive polymers", pages 61-88, the disclosure of which is incorporated herein by reference.

The coloring of the photosensitive polymeric microparticles may be carried out by adding a non-photosensitive dye and/or pigment to the polymerizable component and/or microparticles so that the microparticles develop color. Examples of non-photosensitive dyes and pigments include a variety of organic or inorganic materials known to those skilled in the art. Examples of non-photosensitive dyes include fixed toners such as soluble and dispersible toners, examples of pigments include organo-metallic oxides, and powders and organic pigments such as animal, vegetable or synthetic pigments. The aforementioned non-photosensitive organic dyes and pigments may also be polymerizable using, as an example, a dichroic material, as described below.

Examples of organic pigments include quinacridones, phthalocyanines, isoindolines, anthrapyrimidines, benzanthrones, flavanthrones, peryleneketones, peryleneanthrones, substituted derivatives thereof, and mixtures thereof. Examples of inorganic pigments include titanium dioxide, iron oxide, chromium oxide, lead chromate, carbon black, or mixtures thereof.

The photopolymer microparticles of the present invention can be made at least partially polarizing by adding photochromic-dichroic materials and/or conventional dichroic materials as described previously and orienting them at least partially. Dichroic materials can absorb one of the two orthogonal plane polarization components of transmitted radiation more strongly than the other. The dichroic material is thus capable of linearly polarizing at least part of the transmitted radiation. However, while dichroic materials are capable of preferentially absorbing one of the two orthogonal plane-polarized components of transmitted radiation, if the molecules of the dichroic compound are not properly positioned or arranged, a net linear polarization of the transmitted radiation will not be achieved. That is, due to the random positioning of the dichroic material molecules, the selective absorption of the individual molecules will cancel each other out, such that a net or overall linear polarization effect cannot be achieved. Thus, it is often desirable to properly position or arrange, for example, at least partially orient, dichroic material molecules within another material to form a conventional linear polarizing element. Dichroic materials are oriented, for example, by stretching a polymer sheet to produce a linear polarizing filter or lens for solar mirrors, as is known to those skilled in the art.

Examples of suitable conventional dichroic materials include azomethine, indigo, thioindigo, anthocyanins, indanes, quinophthalone dyes, perylenes, phthalidopterines, triphendioxazines, indoloquinolines, imidazole-triazines, tetrazines, azo and (poly) azo dyes, benzoquinones, naphthoquinones, anthraquinones and (poly) anthraquinones, anthrapyrimidines, iodine and iodates. The dichroic material may be a polymerizable dichroic material. That is, the dichroic material can include at least one polymerizable group. For example, although not limited thereto, the at least one dichroic material may have at least one alkoxy, polyalkoxy, alkyl, or polyalkyl substituent terminated by at least one polymerizable group.

The phrase "subjecting a material to conditions sufficient to at least partially form microparticles" referred to in various methods of preparing a non-aqueous dispersion of photosensitive microparticles includes subjecting the material to conditions of high shear stress to granulate the material into microparticles. High shear stress may be achieved by any high shear stress technique known to those skilled in the art.

As used herein, the term "high shear stress conditions" is meant to include not only high shear stress techniques, such as the liquid-liquid impact techniques discussed in detail below, but also high shear by mechanical means. It is to be understood that any mode of applying stress to the aqueous composition may be employed, as desired, so long as sufficient stress is applied to achieve granulation of the aqueous composition to form microparticles.

Aqueous compositions may be prepared by using Microfluidics Corpor available from Massachusetts, NewtonOf the formation ofThe emulsifier is subjected to suitable shear stress conditions.High pressure impact emulsifiers are described in detail in U.S. Pat. No. 4,533,254, which is incorporated herein by reference. The apparatus is operated at high pressure (up to about 1.4x 10)⁵kPa (20,000psi)) pump and a reaction chamber in which emulsification is performed. In one example, a pre-emulsion of the blend is prepared and then subjected to high shear stress. The pump forces the blend into the chamber where it is divided into at least two streams which pass through at least two slits and impinge at very high velocities such that small particles are formed, e.g., "granulated".

Each aqueous composition is typically at about 3.5x 10⁴About 1x 10⁵The pressure of kPa (5,000 and 15,000psi) is passed through the emulsifier multiple times or until at least partially formed microparticles are produced. Multiple passes of each aqueous composition through the emulsifier can result in microparticles having a smaller average particle size and a narrower particle size distribution range. When using the foregoingWhen emulsifying agents are used, stress is applied by liquid-liquid impact. As noted above, stress may be applied to the pre-emulsified blend in other ways, so long as sufficient stress is applied to achieve at least partially formed microparticles that can be further reduced in size through multiple treatments. For example, an alternative method of applying high shear stress conditions is to use ultrasonic energy, a homogenizer, a rotor/stator mixer, and/or a jet disperser.

Polymerization of the polymerizable component of the at least partially formed photopolymer microparticles can be achieved by irradiating the composition with an initiating amount of radiation and/or adding an initiating amount of a material to the composition, such as an initiator capable of polymerizing by methods such as free radical polymerization, thermal polymerization, photopolymerization, or a combination thereof. Methods of polymerizing the materials used to prepare the photopolymer microparticles of the present invention are well known to those skilled in the art and any of the known techniques described above can be used.

For example, the polymerizable component may be at least partially polymerized by thermal polymerization, such as at a temperature of 22 ℃ to 150 ℃, by photopolymerization, or a combination of the two methods. While a temperature range for thermal polymerization of the polymerizable component in the at least partially formed microparticles is illustrated, one skilled in the art will appreciate that temperatures other than those disclosed herein may be employed.

Methods of initiating polymerization by radiation include the use of ultraviolet, visible, infrared, microwave, gamma or electron beam radiation to initiate polymerization of the polymerizable component. This may be followed by a thermal step to cure any unreacted polymerizable material.

Polymerization of the polymerizable component can be achieved by including an initiating amount of a material capable of generating free radicals, such as an organic peroxy compound or azobis (organonitrile) compound, e.g., an initiator, in the aqueous composition. Examples of suitable organic peroxy compounds that may be used as thermal polymerization initiators include: t-butyl hydroperoxide, peroxy monocarbonates, such as isopropyl t-butyl peroxy carbonate; peroxy dicarbonates, such as di (2-ethylhexyl) peroxy dicarbonate, di (sec-butyl) peroxy dicarbonate and diisopropyl peroxy dicarbonate; diacyl peroxides, such as 2, 4-dichlorobenzoyl peroxide, isobutyryl peroxide, decanoyl peroxide, lauroyl peroxide, propionyl peroxide, acetyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide; peroxy esters, such as t-butyl peroxypivalate, t-butyl peroxyoctoate, and t-butyl peroxyisobutyrate; methyl ethyl ketone peroxide, acetyl cyclohexane sulfonyl peroxide. Preferred among the thermal initiators are those that do not discolor the resulting polymer microparticles and can participate in redox initiator systems that do not require additional heat, as is known to those skilled in the art. See, for example, "Redox Polymerization", G.S.Misra, prog.Polymer.Sci.Vol 8, pp.61-131, 1982, the disclosures of which are incorporated herein by reference.

Examples of suitable azobis (organonitrile) compounds that may be used as thermal polymerization initiators include: 2,2 '-azobis (2, 4-dimethylpentanenitrile), 1' -azobiscyclohexanecarbonitrile, azobisisobutyronitrile, or mixtures thereof.

The amount of thermal polymerization initiator used to initiate and polymerize the polymerizable component can vary and depends on the particular initiator used. Only the amount needed to initiate and maintain the polymerization reaction is needed. The initiator may be used in an amount of 0.01 to 5.0 parts per 100 parts of the polymerizable component (phm) relative to the azobis (organonitrile) compound. Typically, the thermal cure cycle involves heating the polymerizable components in the presence of an initiator for 20 minutes to 2 hours to a temperature in the range of room temperature up to 125 ℃. While a time frame for thermal polymerization of the polymerizable component in the at least partially formed microparticles is illustrated, one skilled in the art will appreciate that time intervals other than those disclosed herein may be used.

Photopolymerization of the polymerizable component can be carried out using ultraviolet light and/or visible light in the presence of a photoinitiator.

Examples of the photoinitiator that can be used in the present invention include cleavage type photoinitiators and hydrogen abstraction type photoinitiators.

Examples of cleavage-type photoinitiators include acetophenone, alpha-aminoalkylphenones, benzoin ethers, benzoyl oximes, acyl phosphine oxides and diacyl phosphine oxides or mixtures of the initiators. A commercially available example of such a photoinitiator is4265 available from ciba chemicals, Inc. Examples of hydrogen abstraction-type photoinitiators include benzophenones, Michler's ketones, thioxanthones, anthraquinones, camphor, fluorenones, coumarins or mixtures of such initiators.

Hydrogen abstraction photoinitiators typically work better in the presence of materials such as amines and other hydrogen donor materials added to provide labile hydrogen atoms for abstraction. Typical hydrogen donors are active hydrogens positioned alpha to the oxygen or nitrogen, such as alcohols, ethers, and tertiary amines, or active hydrogen atoms directly attached to sulfur, such as thiols. In the absence of such added materials, photoinitiation can still be carried out by hydrogen abstraction from the monomer, oligomer or other components of the system.

Cationic photoinitiators may also be used in combination with the aforementioned photoinitiators. Examples of cationic initiators for use with hydrogen abstraction-type photoinitiators are hydrogen donor materials, such as butyryl chloride triphenylbutyl borate, or combinations of such materials. A further example of a cationic photoinitiator is an onium salt, which is described in U.S. patent No. 5,639,802, column 8, line 59-column 10, line 46, the disclosure of which is incorporated herein by reference.

The amount of photopolymerization initiator used to initiate and polymerize the polymerizable component of the at least partially formed microparticles can vary and depends on the particular initiator used. Only the amount needed to initiate and maintain the polymerization reaction is needed. The photopolymerization initiator may be used in an amount of 0.01 to 5% by weight, based on the weight of the polymerizable component.

The light source for photopolymerization is selected from those emitting ultraviolet light and/or visible light. The light source may be a mercury lamp, a mercury lamp doped with FeI3 and/or GaI3, a germicidal lamp, a xenon lamp, a tungsten metal halide lamp, or a combination of such lamps. Typically, the absorption spectrum of the photoinitiator or combination of photoinitiators matches the spectral output of the bulbs, e.g., H, D, Q, and/or V bulbs, to achieve the highest curing efficiency. The exposure time may vary depending on the wavelength and intensity of the light source, the photoinitiator, and the polymerizable component. The at least partially formed microparticles may also be at least partially polymerized using an electron beam process that does not require the presence of an initiator.

Further descriptions of initiators and methods for polymerizing polymerizable components in photosensitive microparticles using thermal and/or photopolymerization methods are disclosed in U.S. Pat. No. 6,602,603 at column 11, line 1 to column 13, line 36, and U.S. Pat. No. 7,001,952 at column 11, line 15 to line 50, the disclosures of which are incorporated herein by reference.

The present invention also provides curable, photosensitive film-forming compositions prepared from (a) a film-forming component comprising at least one hair material having reactive functional groups and (b) a non-aqueous dispersion of photosensitive polymeric microparticles, such as any of those described above. The film-forming composition is typically solvent-based; suitable solvents include those known in the art of coating formulations, for example alcohols such as butanol; ketones, such as methyl amyl ketone; AROMATIC hydrocarbons, such as xylene, AROMATIC/SOLVESSO 100, blends of AROMATIC solvents, available from Exxon Mobil Chemicals; and glycol ethers such as alkylene glycol monoalkyl or dialkyl ethers; esters such as alkoxyalkyl acetates; and mixtures of any of the foregoing.

The film-forming component (a) may comprise a compound of the formula R_xM(OR')_z-xWherein R is an organic group, M is silicon, aluminum, titanium, and/or zirconium, each R' is independently an alkyl group, z is the valence of M, and x is a number less than z and may equal zero. The alkoxides may be used to prepare sol-gel, i.e. solution-gel, coatings. Examples of suitable organic groups include, but are not limited to, alkyl, vinyl, methoxyalkyl, phenyl, 3-glycidoxypropyl, and 3-methacryloxypropyl. The alkoxide may be further mixed and/or reacted with other compounds and/or polymers known in the art. Particularly suitable are compositions comprising siloxanes formed by at least partial hydrolysis of organoalkoxysilanes. Examples of suitable alkoxide-containing compounds and methods for preparing them are described in U.S. patent nos. 6,355,189; 6,264,859, respectively; 6,469,119, respectively; 6,180,248, respectively; 5,916,686, respectively; 5,401,579, respectively; 4,799,963, respectively; 5,344,712, respectively; 4,731,264, respectively; 4,753,827, respectively; 4,754,012, respectively; 4,814,017, respectively; 5,115,023, respectively; 5,035,745, respectively; 5,231,156, respectively; 5,199,979, respectively; and 6,106,605. The alkoxides and their preparation are described in detail in U.S. patent application publication No. 20060246305 [0015 ]]-[0023]Paragraphs, which are hereby incorporated by reference. The use of such alkoxides can reduce interference and provide a refractive index contrast between the film-forming composition and the substrateAnd, at a minimum, particularly when the substrate is a high refractive index optical grade substrate as described below.

In addition, or in addition, the film-forming component (a) may comprise any of the above listed crosslinking materials, such as aminoplasts, including self-condensing aminoplasts.

The film-forming component (a) may comprise a thermosetting polymeric material, a thermoplastic polymeric material or a mixture of said polymeric materials. For example, the film-forming component (a) may comprise a thermosetting polymeric material selected from polyurethanes, polyols in combination with blocked or free polyisocyanates, poly (urea-urethanes), aminoplast resins, polysiloxanes, polyanhydrides, polyacrylamides, epoxy resins or poly (meth) acrylates, such as polymethacrylates, polyacrylates or mixtures thereof. The film-forming component (a) may comprise one or more different ethylenically unsaturated monomers, curable using actinic radiation such as UV radiation.

When the film-forming component (a) comprises a polyol in combination with a blocked or free polyisocyanate, there are many and wide variations of polyisocyanates which may be used. Examples may include aliphatic polyisocyanates, cycloaliphatic polyisocyanates wherein one or more isocyanate groups are directly attached to a cycloaliphatic ring, cycloaliphatic polyisocyanates wherein one or more isocyanate groups are not directly attached to a cycloaliphatic ring, aromatic polyisocyanates wherein one or more isocyanate groups are directly attached to an aromatic ring, and aromatic polyisocyanates wherein one or more isocyanate groups are not directly attached to a cycloaliphatic ring, and mixtures thereof. When using aromatic polyisocyanates, care should generally be taken to select materials which do not cause a color (e.g. yellow) in the polyurethane-containing material tapes.

The polyisocyanate may include aliphatic or cycloaliphatic diisocyanates, aromatic diisocyanates, their cyclic dimers and cyclic trimers, and mixtures thereof. Examples of suitable polyisocyanates may include, Desmodur N3300 (hexamethylene diisocyanate trimer), which is commercially available from Bayer; desmodur N3400 (60% hexamethylene diisocyanate dimer and 40% hexamethylene diisocyanate trimer). Also suitable are Tr ixene BL7960, blocked isocyanates, available from Baxenden Chemicals, Ltd. The polyisocyanate may include dicyclohexylmethane diisocyanate and isomer mixtures thereof. As used herein and in the claims, the term "isomer mixture" refers to a mixture of trans-trans, cis-cis, and/or trans-cis isomers of polyisocyanates. Examples of the isomer mixture used in the present invention may include cis-cis isomer of 4,4' -methylenebis (cyclohexyl isocyanate), hereinafter referred to as "PICM" (p-isocyanatocyclohexyl methane), trans-cis isomer of PICM, trans-trans isomer of PICM, and mixtures thereof.

Suitable isomers for use in the present invention include the following three isomers of 4,4' -methylenebis (cyclohexylisocyanate).

PICM may be prepared by methods well known in the art such as those disclosed in us patent 2,644,007; 2,680,127 and 2,908,703, which are incorporated herein by reference, are prepared by phosgenating 4,4' -methylenebis (cyclohexylamine) (PACM). After phosgenation, the PACM isomer mixture may produce PICM in the liquid phase, partially liquid phase, or solid phase at room temperature. Alternatively, the PACM isomer mixture may be obtained by hydrogenation of methylenedianiline and/or by fractional crystallization of the PACM isomer mixture in the presence of water and alcohols such as methanol and ethanol.

Other aliphatic and cycloaliphatic diisocyanates that may be used include 3-isocyanato-methyl-3, 5, 5-trimethylcyclohexyl-isocyanate ("IPDI"), which is available from Arco chemical, and m-tetramethylxylene diisocyanate (1, 3-bis (1-isocyanato-1-methylethyl) -benzene), which is available under the trade name(Meta) aliphatic isocyanates are available from Cytec industries Inc.

As used herein and in the claims, the term "aliphatic and cycloaliphatic diisocyanates" refers to 6 to 100 carbon atoms, linked in a straight chain or cyclic, having two diisocyanate-reactive end groups. Aliphatic and cycloaliphatic diisocyanates for use in the present invention may include TMXDI and the formula R- (NCO)₂Wherein R represents an aliphatic group or a cycloaliphatic group.

The polyol in film-forming component (a) can include compounds having at least two active hydrogen groups including OH groups and can additionally include primary amine groups, secondary amine groups, thiol groups, and/or combinations thereof. Typically a single multifunctional compound having only OH groups is used; similarly, a single polyfunctional compound having a mixture of functional groups may be used.

Suitable OH-containing materials for use in preparing the polyurethane material of the film-forming component of the present invention may include polyether polyols, polyester polyols, polycaprolactone polyols, polycarbonate polyols, and mixtures thereof.

Examples of polyether polyols are polyalkylene ether polyols, including those having the following structural formula:

wherein the substituent R1 is hydrogen or lower alkyl containing 1 to 5 carbon atoms, including mixed substituents, n is typically 2 to 6 and m is 8 to 100 or higher. Included are poly (oxytetramethylene) glycol, poly (oxytetraethylene) glycol, poly (oxy-1, 2-propylene) glycol, and poly (oxy-1, 2-butylene) glycol.

Examples of epoxides may include ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, aralkylene oxides such as, but not limited to, styrene oxide, mixtures of ethylene oxide and propylene oxide. Polyoxyalkylene polyols may be prepared by a mixture of alkylene oxides using random or stepwise oxyalkylation.

Also useful are polyether polyols formed by the oxyalkylation of various polyols, for example, diols such as ethylene glycol, 1, 6-hexanediol, bisphenol A, and the like, or other higher polyols such as trimethylolpropane, pentaerythritol, and the like. The useful higher functionality polyols can be prepared, for example, by oxyalkylation of compounds such as sucrose or sorbitol. One commonly used oxyalkylation method is the reaction of a polyol with an alkylene oxide such as propylene oxide or ethylene oxide in the presence of an acidic or basic catalyst. Specific polyethers include those sold under the names TERATHANE and TERACOL, available from E.I. Du Pont de Nemours and Company, Inc., and POLYMEG, available from Q O Chemicals, Inc., a subsidiary of Great Lakes chemical Corp.

The polyether glycol used in the present invention may include, but is not limited to, polytetramethylene ether glycol.

The polyether containing polyol may include a block copolymer alkane comprising ethylene oxide-propylene oxide and/or ethylene oxide-butylene oxide blocks. Pluronic R, Pluronic L62D, Tetronic R and Tetronic, available from BASF, may be used as the polyol-containing polyether material in the present invention.

Suitable polyester diols may include the esterification products of one or more dicarboxylic acids having 4 to 10 carbon atoms, such as adipic acid, succinic acid or sebacic acid, with one or more low molecular weight diols having 2 to 10 carbon atoms, such as ethylene glycol, propylene glycol, diethylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 6-hexanediol and 1, 10-decanediol. The polyester diol may be the esterification product of adipic acid with a diol of 2 to 10 carbon atoms.

Suitable polycaprolactone diols for use in the present invention may include the reaction product of E-caprolactone with one or more of the low molecular weight diols listed above. The polycaprolactone can be obtained by reacting caprolactone with a difunctional active hydrogen compound such as water orBy condensation in the presence of at least one of the low molecular weight diols listed above. Specific examples of polycaprolactone diols include polycaprolactone polyester diols, which may be mentioned as2047 and2077 was purchased from Solvay Corp.

Polycarbonate polyols are known in the art and are commercially available, such as ravecarb 107(Enichem s.p.a.). Polycarbonate polyols can be prepared by reacting an organic diol, such as a diol, with a dialkyl carbonate, as described in U.S. Pat. No. 4,160,853. The polyol may include, for example, a poly-hexamethylcarbonate having various degrees of polymerization.

The diol material may include low molecular weight polyols, such as polyols having a molecular weight of less than 500, and compatible mixtures thereof. As used herein, the term "compatible" means that the diols are miscible with each other to form a single phase. Examples of such polyols may include low molecular weight diols and triols. If used, the amount of triol is selected to avoid a high degree of crosslinking in the polyurethane. A high degree of crosslinking can result in a curable polyurethane that cannot be formed by mild heat and pressure. The organic diol typically contains 2 to 16, or 2 to 6, or 2 to 10 carbon atoms. Examples of such diols may include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, monopropylene glycol, tripropylene glycol, 1,2-, 1, 3-and 1, 4-butanediol, 2, 4-trimethyl-1, 3-pentanediol, 2-methyl-1, 3-pentanediol, 1,3-, 2, 4-and 1, 5-pentanediol, 2, 5-and 1, 6-hexanediol, 2, 4-heptanediol, 2-ethyl-1, 3-hexanediol, 2-dimethyl-1, 3-propanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, 1, 2-bis (hydroxyethyl) -cyclohexane, glycerol, tetramethylolmethane such as but not limited to pentaerythritol, trimethylolethane and trimethylolpropane; and their isomers.

The OH-containing material can have a weight average molecular weight of, for example, at least 60, or at least 90, or at least 200. Further, the OH-containing material can have a weight average molecular weight of, for example, less than 10,000, or less than 7000, or less than 5000, or less than 2000.

The OH-containing material used in the present invention may include triesters made from at least one low molecular weight dicarboxylic acid, such as adipic acid.

The polyesterdiols and polycaprolactone diols used in the present invention can be prepared using known esterification or transesterification methods, as described, for example, in "Polyester from Lactone" by D.M. Young, F.Hostettler et al, Union Carbide F-40, page 147.

The polyester diol may also be prepared from 1, 6-hexanediol and adipic acid; 1, 10-decanediol and adipic acid; or 1, 10-decanediol and caprolactone.

The multipolymer used in the present invention may be selected from: (a) esterification products of adipic acid with at least one diol selected from 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, or 1, 10-decanediol; (b) a reaction product of E-caprolactone with at least one diol selected from 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, or 1, 10-decanediol; (c) polytetramethylene glycol; (d) an aliphatic polycarbonate diol, and (e) mixtures thereof.

Typically in the film-forming compositions of the present invention, the photopolymer microparticles contain functional groups that are reactive with the reactive functional groups of the materials in the film-forming component (a) so that the microparticles become integrated with the composition. Such functional groups may be any of those discussed above.

The film-forming compositions of the present invention are useful for coating substrates and for preparing photosensitive coated articles. The substrate can be any optical element, such as an optical memory element, a display element, an ophthalmic element, a window element, or a mirror element.

The curable film-forming compositions of the present invention typically exhibit a refractive index of greater than 1.5, typically from 1.55 to 1.65, and more typically from 1.58 to 1.60, after application to a substrate and curing.

The substrate may comprise an at least partially cured polymeric organic material selected from a thermosetting polymeric organic material, a thermoplastic polymeric organic material or a mixture of said polymeric organic materials. In other embodiments of the invention, the polymeric organic material is selected from poly (C1-C12 alkyl methacrylate), poly (oxyalkylene dimethacrylate), poly (alkoxylated phenol methacrylate), cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly (vinyl acetate), poly (vinyl alcohol), poly (vinyl chloride), poly (vinylidene chloride), thermoplastic polycarbonate, polyester, polyurethane, polythiourethane, polysulfone thiourethane, poly (urea-urethane), poly (ethylene terephthalate), polystyrene, poly (alpha-methyl styrene), copoly (styrene-methyl methacrylate), copoly (styrene-acrylonitrile), polyvinyl butyral, or a copolymer of bis (allyl carbonate) monomer, poly (vinyl acetate butyrate), poly (vinyl acetate), poly (vinyl alcohol), poly (vinyl chloride), poly (vinylidene chloride), thermoplastic polycarbonate, polyester, poly (vinyl chloride), poly (vinyl acetate), poly (ethylene terephthalate), poly (alpha-methyl styrene-co-methyl methacrylate), a multifunctional acrylate monomer, a multifunctional methacrylate monomer, a diethylene glycol dimethacrylate monomer, a diisopropenyl benzene monomer, an ethoxylated bisphenol a dimethacrylate monomer, a ethylene glycol dimethacrylate monomer, a poly (ethylene glycol) dimethacrylate monomer, an ethoxylated phenol dimethacrylate monomer, an alkoxylated polyhydric alcohol polyacrylate monomer, a styrene monomer, a urethane acrylate monomer, a glycidyl methacrylate monomer, a diallylidene pentaerythritol monomer, or a mixture of said monomers.

Suitable substrates for making the optical elements of the present invention have a refractive index of at least 1.55 and include non-plastic substrates such as glass. More generally, substrates commonly used for optical applications are used, including polyol (allyl carbonate) monomers, for example, allyl diglycol carbonates such as diethylene glycol bis (allyl carbonate), which are sold under the trademark CR-39 by PPG Industries, Inc; polyurea-polyurethane (polyureaurethane) polymers, for example prepared by reaction of a polyurethane prepolymer and a diamine curing agent, one such polymer composition being sold under the trademark TRIVEX by PPG Industries, Inc; a polyol (meth) acryloyl terminated carbonate monomer; diethylene glycol dimethacrylate monomer; ethoxylated phenol methacrylate monomers; diisopropenyl benzene monomer; ethoxylated trimethylolpropane triacrylate monomer; ethylene glycol dimethacrylate monomer; a poly (ethylene glycol) dimethacrylate monomer; a urethane acrylate monomer; poly (ethoxylated bisphenol a dimethacrylate); polyvinyl acetate; polyvinyl alcohol; polyvinyl chloride; poly (vinylidene chloride); polyethylene; polypropylene; a polyurethane; a polythiourethane; thermoplastic polycarbonates, such as carbonate-linked resins derived from bisphenol a and phosgene, one such material being sold under the trademark LEXAN; polyester, such as the material sold under the trademark MYLAR; poly (ethylene terephthalate); polyvinyl butyral; poly (methyl methacrylate), such as the material sold under the trademark PLEXIGLAS, and polymers prepared by homopolymerization or copolymerization and/or terpolymerization of polyfunctional isocyanates with polythiols or polyepisulfide monomers with polythiols, polyisocyanates, polyisothioisocyanates, and optionally ethylenically unsaturated monomers or halogenated aromatic-containing vinyl monomers. Also encompassed are copolymers of the above monomers, and blends of the polymers, and copolymers with other polymers, for example to form interpenetrating network products. Typically, the refractive index of the substrate is from 1.55 to 1.67, usually from 1.55 to 1.65. Thiopolyurethanes, polycarbonates, and/or sulfur-based polyurethaneureas are the most commonly used substrates.

The optical element includes: optical storage elements such as devices for optical storage and image processing; ophthalmic elements such as corrective lenses, non-corrective lenses, contact lenses, intraocular lenses, magnifying glasses, protective lenses, and goggles (visors); window elements such as transparencies, filters, gratings, and optical switches for buildings, automobiles, motorcycles, and aircraft; a mirror element; and display elements such as screens, displays, liquid crystal cells, organic light emitting devices, and security elements.

The term "optical" as used herein means relating to or relating to light and/or vision. The optical storage element may include an image processing device and an optical data storage device. In such optical storage elements, the interaction of the device with the optical signal causes a change in the optical memory of the device over a period of time until there is a change in the form in which the image is processed or retained, or until there is a change in the form in which information is retained for further alteration or deletion. The term "ophthalmic" as used herein refers to a condition associated with or related to the eye and vision. Examples of ophthalmic elements include corrective and non-corrective lenses, including monofocal or multifocal lenses, which may be segmented or non-segmented multifocal lenses (such as, but not limited to, bifocal lenses, trifocal lenses, and progressive lenses), as well as other elements for correcting, protecting, or improving (decorative or otherwise) vision, including, but not limited to, contact lenses, intraocular lenses, magnifying lenses, and protective lenses or goggles.

The term "window" as used herein refers to an opening adapted to allow transmission of radiation therethrough. Examples of windows include transparencies for buildings, automobiles, and aircraft, filters, gratings, and optical switches. The term "mirror element" as used herein refers to a surface that specularly reflects a substantial portion of incident light. In the present invention, the reflected light may be changed by the type of photopolymer microparticles attached to the mirror element.

The term "display" as used herein refers to a visual or machine-readable representation of information in the form of words, numbers, symbols, designs or graphics. Examples of display elements and devices include screens, displays, liquid crystal cells, organic light emitting devices, and security elements. The term "liquid crystal cell" as used herein refers to a structure containing a liquid crystal material as an anisotropic material capable of ordering. An active liquid crystal cell is a cell in which the liquid crystal material can be switched between an ordered and an unordered state, or between two ordered states, by application of an external force, such as an electric or magnetic field. A passive liquid crystal cell is a cell in which the liquid crystal material remains in an ordered state. An example of an active liquid crystal cell element or device is a liquid crystal display.

The term "ordering" as used herein means to bring about a suitable arrangement or position, for example, by orientation with another structure or material, or by some other force or effect. Thus, the term "ordering" as used herein encompasses both a contact method of ordering a material, such as orienting with another structure or material, and a non-contact method of ordering a material, such as exposure to an external force or effect. The term "ordering" also encompasses a combination of contact and non-contact methods.

Examples of methods of at least partially ordering liquid crystal materials and other anisotropic materials such as nonlinear optical materials, photochromic-dichroic materials, and dichroic dyes, according to various embodiments disclosed herein, using liquid crystal materials as an example, include exposing at least a portion of the liquid crystal material to at least one of: magnetic field, electric field, linearly polarized infrared radiation, linearly polarized ultraviolet radiation, linearly polarized visible radiation, and shear force.

In addition to the foregoing methods of at least partially ordering the liquid crystal material, the liquid crystal material may be at least partially ordered by orienting at least a portion of the liquid crystal material with another material or structure, such as an orientation device. The term "orientation means" as used herein refers to a mechanism that can facilitate the positioning of one or more other structures exposed to at least a portion of the mechanism. Further information on the orientation device is disclosed in U.S. patent application Ser. No. P-108,935, paragraphs [0153] - [0288], filed 5, month 17, 2004, the disclosure of which is incorporated herein by reference.

The optical element is typically selected from an optical storage element, a display element, an ophthalmic element, a window element or a mirror element. The display element is typically selected from a screen, a display, a liquid crystal cell, an organic light emitting device or a security element. In a particular embodiment, the optical element is an organic light emitting device "OLED", wherein the first surface is an anode, the second surface is a cathode and the material positioned therebetween is a light emitting material, the light emitting material being in electrical contact with the anode and the cathode.

When current is applied to the OLED, the anode injects holes and the cathode injects electrons into a light emitting material comprising an effective amount of the photosensitive polymer microparticles of the present invention. The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and a hole are localized on the same molecule, an "exciton," which is a localized electron-hole pair with an excited energy state, is formed. Light is emitted when the exciton relaxes by a luminescence mechanism known to those skilled in the art. See, for example, U.S. patent 6,687,266, column 2, line 47-column 18, line 59, the disclosure of which is incorporated herein by reference. In these cases, the at least partially crosslinked photopolymer microparticles typically comprise an effective amount of a photosensitive material selected from fluorescent materials, phosphorescent materials, or mixtures thereof.

Examples of security elements include articles having incorporated and or attached to at least a portion of at least one surface of the article an effective amount of at least partially crosslinked photopolymer microparticles of the present invention. An effective amount of photopolymer microparticles is an amount of the microparticles that will identify the article. An effective amount of photosensitive microparticles may be localized in the identifying mark. Examples of such secure elements include, but are not limited to: access and pass cards such as tickets, badge, identification or membership cards, debit cards, and the like; negotiable securities and non-negotiable securities, such as money orders, checks, bonds, banknotes, deposit documents, stock documents, and the like; official documents such as currency, licenses, identification cards, welfare cards, visas, passports, official certificates, deeds, and the like; consumer goods, such as software, compact discs ("CDs"), digital video discs ("DVDs"), appliances, consumer electronics, sporting products, automobiles, and the like; a credit card; or shopping tags, labels and packaging.

The security element may be attached to at least a portion of a substrate selected from the group consisting of transparent substrates and reflective substrates. Alternatively, when a reflective substrate is desired, if the substrate is not reflective or is not sufficiently reflective for the intended application, a reflective material may first be applied to at least a portion of the substrate prior to application of the authenticating mark. For example, an at least partially reflective aluminum coating may be applied to at least a portion of the substrate and then the security element formed thereon. Still further, the security element may be attached to at least a portion of a substrate selected from the group consisting of an untinted substrate, a tinted substrate, a photochromic substrate, a tinted photochromic substrate, an at least partially linearly polarized, an at least partially circularly polarized substrate, and an at least partially elliptically polarized substrate. In some cases, the security element is a security element that is at least partially linearly polarized.

In addition, the security element may further comprise one or more other coatings or sheets to form a multilayer reflective security element having viewing angle dependent properties, as described in U.S. patent 6,641,874, column 1, line 6 to column 13, line 28, which is incorporated herein by reference.

The term "at least partially linearly polarize" as used herein when modifying a coating or substrate refers to a coating or substrate that is adapted to linearly polarize radiation (e.g., to confine some or all of the vibrations of the electric field vector of a light wave to one direction). The term "at least partially circularly polarizing" as used herein when modifying a coating or substrate refers to being adapted to circularly polarize some or all of the radiation. The term "at least partially elliptically polarize" as used herein when modifying a coating or substrate refers to a coating or substrate that is suitable for elliptically polarizing some or all of the radiation. As used herein, the term "photochromic" when modifying a coating or substrate refers to a coating or substrate having an absorption spectrum of visible radiation that changes in response to at least actinic radiation. In addition, as used herein, the term "tinted photochromism" when modifying a substrate refers to a substrate that contains a colorant and a photochromic material that has an absorption spectrum for at least visible, ultraviolet, and/or infrared radiation that changes in response to actinic radiation. Thus, for example, a tinted photochromic substrate may have a first color characteristic of a colorant and a second color characteristic of a combination of the colorant and the photochromic material when exposed to actinic radiation.

Methods of applying the film-forming compositions of the present invention include methods known in the art for applying coatings such as spin coating, spray and spin coating, curtain coating, flow coating, dip coating, injection molding, casting, roll coating, wire coating, and overmolding. According to one example, an at least partial coating comprising photopolymer microparticles is applied to a mold, for example by overmolding the substrate onto the coating or placing a preformed substrate onto the coating, and the coating is at least partially cured. In such cases, the coating may be applied as a liquid or powder coating comprising photopolymer microparticles. Photochromic articles comprising the polymeric sheets described below can also be prepared using an over-molding process.

The coated substrate may further comprise additional coatings such as primer coatings, abrasion resistant coatings, antireflective coatings, transitional coatings disposed between the photosensitive coating and the abrasion resistant coating, at least partially polarized polymeric films or coatings, and combinations thereof.

As noted above, in some cases, a primer coating is applied to the substrate surface followed by application of a curable film-forming composition. The primer coating is disposed between the substrate and the curable film-forming composition and functions as a barrier coating that prevents the polymeric coating components and the substrate from interacting with each other and/or as an adhesion layer that promotes adhesion of the curable film-forming composition to the surface of the substrate. The primer may be applied to the substrate by any known method, such as spray coating, spin coating, spread coating, curtain coating, roll coating, or dip coating; and may be applied to cleaned and untreated, or cleaned and treated (e.g., chemically or plasma treated) substrate surfaces. Primer coatings are known to those skilled in the art. The selection of a suitable primer coating depends on the substrate used, i.e., the primer coating must be chemically and physically compatible with the substrate surface and the curable film-forming composition, while providing the functional benefits desired for the primer coating, i.e., barrier and adhesion properties.

The primer coating may be one or several monolayers thick and may range from 0.1 to 10 microns, more typically 0.1 to 2 or 3 microns. The thickness of the primer can vary between any combination of the foregoing values, including the recited values. One contemplated embodiment of a suitable primer coating comprises an organofunctional silane, such as methacryloxypropyltrimethoxysilane, a catalyst material that generates an acid upon exposure to actinic radiation, e.g., an onium salt, and an organic solvent, such as diglyme or isopropyl alcohol, as described in U.S. Pat. No. 6,150,430, the disclosure of which is incorporated herein by reference.

A further example of a primer coating is described in U.S. patent 6,025,026, which describes a composition that is substantially free of organosiloxanes but comprises an organic anhydride having at least one olefinic linkage and an isocyanate-containing material. This disclosure is also incorporated herein by reference. After the primer is applied, the substrate may be rinsed with an alcohol such as 2-propanol, followed by water, and dried at 60 ℃ to 80 ℃ for up to half an hour.

The aforementioned coating may be attached to at least a portion of the same surface of the substrate in the following order from the surface: primer layer, photosensitive layer, transition layer, abrasion resistant layer, polarizing film or coating, anti-reflective layer, abrasion resistant layer; or a primer layer, a photosensitive layer, a transition layer, an abrasion resistant layer, and an anti-reflective layer; or a photosensitive layer, a transition layer, and a polarizing layer; or a primer layer, a photosensitive layer, and a polarizing layer; or a primer layer, a photosensitive layer, and an anti-reflective layer. Many different combinations of the aforementioned coatings are possible, as known to those skilled in the art. All of the foregoing coatings can be applied to one or more surfaces of a substrate, such as both surfaces of an optical substrate. A photosensitive coating is typically applied to one surface. The substrate can be any of the materials described herein as substrates. In one example, the substrate is an optical element. In a particular example, the optical element is an ophthalmic element.

Examples of primer coatings that may be used in the present invention include coatings comprising coupling agents, at least partial hydrolysis products of coupling agents, and mixtures thereof. As used herein, "coupling agent" refers to a material having at least one group capable of reacting, binding, and/or associating with a group on at least one surface. The coupling agent may function as a molecule at the interface of at least two surfaces that may be similar or dissimilar. The coupling agent may be a monomer, a prepolymer and/or a polymer. The materials include organo-metals such as silanes, titanates, zirconates, aluminates, zircoaluminates, their hydrolysates, and mixtures thereof. The phrase "at least partial hydrolysis product of a coupling agent" as used herein means that at least some to all of the hydrolyzable groups on the coupling agent are hydrolyzed. Other examples of suitable primer coatings include those described in U.S. Pat. No. 6,025,026 at column 3, line 3 to column 11, line 40, and U.S. Pat. No. 6,150,430 at column 2, line 39 to column 7, line 58, the disclosures of which are incorporated herein by reference.

As used herein, the term "transitional coating" refers to a coating that contributes to the creation of a property gradient between two coatings. For example, a transitional coating may help create a hardness gradient between a relatively hard coating and a relatively soft coating. Examples of transitional coatings include radiation-cured acrylate-based films, as described in U.S. patent 7,452,611, the disclosure of which is incorporated herein by reference.

Examples of at least partially abrasion resistant and other protective coatings include abrasion resistant coatings comprising organosilanes, organosiloxanes, abrasion resistant coatings based on inorganic materials such as silica, titania, and/or zirconia, organic abrasion resistant coatings of the ultraviolet light energy curable type, oxygen barrier coatings that improve the fatigue resistance of photosensitive materials, UV protective coatings, and combinations thereof.

The phrase "at least partially abrasion resistant coating or sheet" refers to a coating or at least partial sheet of a protective polymeric material having an abrasion resistance greater than that of a standard reference material, such as that available from PPG Industries, IncThe monomers were prepared to produce polymers and tested in a manner comparable to ASTM F-735 Standard test method for abrasion resistance of clear plastics and coatings using the Oscillating Sand method.

The phrase "at least partially antireflective coating" refers to a coating that at least partially improves the antireflective properties of a substrate coated with the coating by reducing the amount of intense light reflection from the surface of the substrate, and, for transparent substrates, increasing the percent light transmittance compared to an uncoated substrate. Examples of antireflective coatings include single or multiple layers of metal oxides, metal fluorides, or other such materials that can be deposited onto the articles of the present invention by vacuum evaporation, sputtering, or other methods.

Examples of at least partially linearly polarizing coatings include, but are not limited to, coatings comprising conventional dichroic compounds such as, but not limited to, those previously discussed.

The present invention is more particularly described in the following examples that are intended as illustrations only, since numerous modifications and variations therein will be apparent to those skilled in the art.

In part I, components a-T represent examples 1-14 that combine and react to produce a non-aqueous nano-dispersion of photochromic microparticles and comparative examples 1 and 2 of aqueous dispersions of materials of photochromic microparticles. In part II, a coating composition incorporating the photochromic microparticles of part I is described, as well as the preparation of the coated lens and the physical testing of the coated lens. In section III, photochromic performance testing on selectively coated lenses is described.

The water used in the examples and comparative examples was deionized water. Gel Permeation Chromatography (GPC) was performed using polystyrene standards whose molecular weights are reported as number average molecular weight (Mn) grams/mole, weight average molecular weight (Mw) grams/mole, and polydispersity index (PDI). Sonication was performed using a Fischer Scientific Model FS30D sonicator at an output frequency of 42KHz and time as indicated. The percent solids test was performed by: a known amount of material was added to the aluminum pan, acetone was added to evenly distribute it on the aluminum pan, heated in an oven at 120 ℃ for 1 hour, and the difference in mass from the initial weight and the calculated percentage were determined. Percent Water analysis by Karl Fischer titration Using Metrohm 758KFD Titrino auto titration System andcomposite 5K reagent.

Part I-materials and methods

Component A-hydrophilic polyurethane prepolymer

The following materials were charged in the order described to a suitably equipped reaction flask such as a four-necked round bottom flask equipped with an electronic temperature probe, mechanical stirrer, condenser, and heating mantle.

Feeding of the feedstock	Material	Weight, g
			A	2, 2-dimethylolpropionic acid	100.6
	Butylated hydroxytoluene	0.9
				Phosphorous acid triphenyl ester	0.9
	Dibutyl tin dilaurate	0.9
				N-methyl pyrrolidone	120.0
			B	SR495B(1)	258.3
			C	Dicyclohexylmethane diisocyanate	393.0
			D	Toluene	376.0
	Diethanolamine (DEA)	78.9
				Toluene	78.9

(1) Reported as caprolactone acrylate, available from Sartomer Company, Inc.

Charge a was stirred in the flask at a temperature of 100 ℃ until all solids were dissolved. Feed B was added and the mixture was reheated to 80 ℃. Feed C was added over 15 minutes, and the resulting mixture was held at 80 ℃ for 3 hours and cooled to below 50 ℃. Charge D and the resulting mixture were added, stirred for 30 minutes, and cooled to below 65 ℃. And (4) room temperature. The final product was an extremely viscous, clear yellow solution.

Component B-hydrophilic polyurethane prepolymer

The following materials were charged in the order described to a suitably equipped reaction flask.

(2) Reported as a poly-functional aliphatic polyisocyanate resin, available from bayer materials Science LLC.

Charge a stirred in the flask at a temperature of 55 ℃ to become a cloudy solution. Feed B was added and the mixture was maintained at 55 ℃. Feed C was added over a period of 15 minutes and the resulting mixture was held at 55 ℃ for 1 hour. The mixture was heated to 60 ℃, held at that temperature for 3 hours, and then the heating bath was removed. Charge D was added and the resulting mixture was stirred for 75 minutes and cooled to below 50 ℃. The final product was a clear viscous solution. The% solids was determined to be 63.32.

Component C-hydrophilic polyurethane prepolymer

The following materials were charged in the order described to a suitably equipped reaction flask.

Charge a stirred in the flask at a temperature of 50 ℃ and became a cloudy solution. Feed B was added and the mixture was maintained at 50 ℃. Feed C was added over a period of 15 minutes and the resulting mixture was held at 50 ℃ for 2.5 hours, the mixture becoming viscous and clear. The heating bath was removed and the mixture was cooled to room temperature. Charge D was added and the resulting mixture was stirred for 30 minutes. The final product was a clear viscous solution. The% solids was determined to be 62.39.

Component D-hydrophilic polyurethane prepolymer

The following materials were charged in the order described to a suitably equipped reaction flask.

Charge a was added to the reaction flask with stirring. The resulting mixture was heated to reflux (80 ℃) and held at this temperature for 20 minutes until the mixture became a clear solution. The mixture was cooled to 65 ℃ and feed B was added dropwise using a dropping funnel. The dropping funnel was rinsed with feed C. The mixture was heated to 75 ℃ and held at this temperature for 4 hours. The resulting mixture was cooled to below 60 ℃ and charge D was added. The mixture was stirred for 30 minutes. The IR spectrum of the example obtained shows no detectable isocyanate. The% solids was 53.51.

Component E-hydrophilic polyurethane prepolymer

The following materials were charged in the order described to a suitably equipped reaction flask.

(3) Reported as bis (4-isocyanatocyclohexyl) methane, available from Bayer materials Science LLC.

Charge A, B and C were added sequentially with stirring to an appropriately equipped reaction flask. The resulting mixture was heated to 80 ℃ and held at this temperature for 5 hours. The resulting mixture was cooled to 60 ℃ and feed B was added. The reaction mixture was cooled and charge C was added. The final product had an acid number of 51, a solids content of 50% and Mn of 1620, based on 100% by weight of resin solids, as determined by gel permeation chromatography.

Component F-hydrophilic polyurethane prepolymer

The following materials were charged in the order described to a suitably equipped reaction flask.

Feeds a and B were added sequentially to a suitably equipped reaction flask with stirring. The resulting mixture was heated to 60 ℃ and feed C was added over 15 minutes. The resulting mixture was heated to 80 ℃ and held at this temperature for 5 hours. The resulting mixture was cooled to 60 ℃ and charge D was added, allowing the reaction mixture to exotherm to 67 ℃. The reaction mixture was cooled and charge E was added. The final product had an acid number of 27, a solids content of 50% and a Mn of 2290, as determined by gel permeation chromatography, based on 100% by weight resin solids.

Component G-hydrophilic polyurethane prepolymer

The following materials were charged in the order described to a suitably equipped reaction flask.

Charge a was added to the appropriately equipped reaction flask in sequence with stirring. The resulting mixture was heated to 100 ℃ and charge B was added. The reaction mixture was cooled to 80 ℃ and feed C was added slowly while keeping the reaction mixture at 80 ℃ for 3 hours. Feed D was added followed by feed E.

Component H-hydrophilic polyurethane prepolymer

Step 1-polycarbonate acrylate oligomer

The following materials were charged in the order described to a suitably equipped reaction flask.

Material	Weight, g
		Hydroxy ethyl methacrylate	32.5
Trimethylene carbonate	229.7
		Methyl hydroquinone	0.05
Methyl radicalEther hydroquinones	0.05
		Tin octylate	0.13

The mixture was heated at 120 ℃ for 20 hours and then cooled. The final product had a solids content of 93.7%, Mn 1601 and Mw 2127 as determined by gel permeation chromatography.

Step 2-hydrophilic polyurethane prepolymer

The following materials were charged in the order described to a suitably equipped reaction flask.

Charge a was added to a suitably equipped reaction flask with stirring. The mixture was heated to 90 ℃ for 5 minutes and cooled to 50 ℃. Feed B was added over 10 minutes, followed by feed C to rinse the dropping funnel. The reaction mixture was heated to 80 ℃ and held at this temperature for 2 hours. Charge D was heated to 60 ℃ in another appropriately equipped reaction flask and the mixture resulting from charges a-C was added, followed by charge E to rinse the reaction flask. The reaction was cooled and charge F was added. The final product had an acid number of 13.7, a% solids of 25.0, a pH of 7.68 and a Brookfield viscosity of 1240cps using a #3 spindle at 50 rpm.

Component I-photochromic hydrophobic polyurethane prepolymers

The following materials were charged in the order described to a suitably equipped reaction flask.

(4) Reported as aliphatic diisocyanates, available from Cognis.

(5) Photochromic A is 3, 3-bis (4-methoxyphenyl) -6,11, 13-trimethyl-13- (2- (2- (2-hydroxyethoxy) ethoxy) -3H, 13H-indeno [2',3':3,4] naphtho [1,2-b ] pyran

Charge a was charged to an appropriately equipped reaction flask. Charge B was added and the mixture was stirred and heated to 90 ℃. After 90 ℃, feed C was added through the dropping funnel and feed D was used to rinse the dropping funnel. After the addition was complete, the resulting mixture was held at 90 ℃ for 1.5 hours. The mixture was cooled to 80 ℃. Charge E was added by bubbling through a pinhole into the mixture. The resulting mixture was heated to 80 ℃ for 1 hour. After cooling, the final product was transferred to a glass jar. The arithmetic mean% solids for the four batches was 51.1%.

Component J-photochromic hydrophobic polyurethane prepolymer

The following materials were charged in the order described to a suitably equipped reaction flask.

Charge a was added to a suitably equipped reaction flask and the mixture stirred and heated to 90 ℃. After 90 ℃ had been reached, feed B was added in portions over 30 minutes, and after the addition was complete, the resulting mixture was held at 90 ℃ for 2 hours. The mixture was cooled to 80 ℃. Feed C was added over 15 minutes and the temperature was maintained at 80 ℃ for 3 hours. After cooling, charge D was added. The% solids was 50.0%.

Component K-hydrophobic polyurethane prepolymer

Step 1-p-caprolactone compatibilized dyes

The following materials were charged in the order described to a suitably equipped reaction flask.

Feeding of the feedstock	Material	Weight, g
			A	Photochromic B(6)	32.5
	Aluminium isopropoxide	3.5
				Dichloromethane (Anhydrous)	260.0
			B	e-caprolactone	64.8
			C	Hydrochloric acid (10wt% solution)	35.0
			D	Dichloromethane (Anhydrous)	120(mL)

(6) Photochromic B is 3- (4-methoxyphenyl) -3- (4- (2-hydroxyethoxy) phenyl) -13, 13-dimethyl-3H, 13H-indeno [2',3':3,4] naphtho [1,2-B ] pyran.

Charge a was added to an appropriately equipped reaction flask and the mixture was dissolved by ultrasonication at room temperature for 10 minutes. The resulting reaction mixture was placed under nitrogen, charge B was added and the reaction mixture was stirred at 32 ℃ for 7 hours. The reaction solution was quenched with feed C. Charge D was added and the resulting mixture was stirred at 32 ℃ for 30 minutes. The reaction mixture was partitioned, and the organic layer was collected, washed with brine (25 g) and dried, and neutralized with sodium hydrogencarbonate (0.5 g), neutral alumina (3 g) and magnesium sulfate. The resulting organic layer was filtered through filter paper and the solvent was removed under vacuum. The final product was a dark purple/red oil with a% solids of 90+%, Mn of 1920 g/mole and PDI of 1.30 as determined by gel permeation chromatography.

Step 2-hydrophobic polyurethane prepolymer

The following materials were charged in the order described to a suitably equipped reaction flask.

Charge a was added to a suitably equipped reaction flask with stirring. The mixture was heated to 90 ℃ and feed B was added in portions over 20 minutes. The resulting mixture was maintained at 90 ℃ and stirred for 1.5 hours. The reaction mixture was cooled to 80 ℃ and charge C was added. The resulting mixture was kept at 80 ℃ under an air atmosphere and cooled to room temperature. The final product was a dark purple/red viscous solution with% solids of 50,0, Mn of 2510 and PDI of 1.42 as determined by gel permeation chromatography.

Component L-hydrophobic polyurethane prepolymer

Step 1-p-caprolactone compatibilized dyes

The following materials were charged in the order described to a suitably equipped reaction flask.

Feeding of the feedstock	Material	Weight, g
			A	Photochromic C(7)	70.0
	Aluminium isopropoxide	6.42
				Dichloromethane (Anhydrous)	525.0
			B	e-caprolactone	131.4
			C	10wt% hydrochloric acid solution	75.0
			D	Dichloromethane (Anhydrous)	250(mL)

(7) Photochromic C is 3- (4-methoxyphenyl) -3- (4- (2-hydroxyethoxy) phenyl) -6, 7-dimethoxy-11-trifluoromethyl-13, 13-dimethyl-3H, 13H-indeno [2',3':3,4] naphtho [1,2-b ] pyran.

Charge a was added to an appropriately equipped reaction flask and the mixture was dissolved by ultrasonication at room temperature for 10 minutes. The resulting reaction mixture was placed under nitrogen, charge B was added and the reaction mixture was stirred at 32 ℃ for 7 hours. The reaction solution was quenched with feed C. Charge D was added and the resulting mixture was stirred at 32 ℃ for 30 minutes. The reaction mixture was partitioned, and the organic layer was collected, washed with brine (50 g) and dried, and neutralized with sodium hydrogencarbonate (0.5 g), neutral alumina (5.0 g) and magnesium sulfate. The resulting organic layer was filtered through filter paper and the solvent was removed under vacuum. The final product was a dark green oil with a% solids of 90+%, Mn of 1950 g/mole and PDI of 1.29 as determined by gel permeation chromatography.

Step 2-hydrophobic polyurethane prepolymer

The following materials were charged in the order described to a suitably equipped reaction flask.

Charge a was added to a suitably equipped reaction flask with stirring. The mixture was heated to 90 ℃ and feed B was added in portions over 20 minutes. The resulting mixture was maintained at 90 ℃ and stirred for 1.5 hours. The reaction mixture was cooled to 80 ℃ and charge C was added. The resulting mixture was kept at 80 ℃ under an air atmosphere and cooled to room temperature. The final product was a dark green slightly viscous solution with a% solids of 50.0, Mn of 2100 and PDI of 1.49 as determined by gel permeation chromatography.

Component M-hydrophobic polyurethane prepolymer

Step 1-p-caprolactone compatibilized dyes

The following materials were added in the order described to a suitably equipped reaction flask

(8) The photochromic material D is 3, 3-bis (4-methoxyphenyl) -6, 11-dimethoxy-13-butyl-13- (2-hydroxyethoxy-3H, 13H-indeno [2',3':3,4] naphtho [1,2-b ] pyran.

Charge a was added to a suitably equipped reaction flask and the mixture was dissolved by ultrasonication at room temperature for 10 minutes. The resulting reaction mixture was placed under nitrogen, charge B was added and the reaction mixture was stirred at 32 ℃ for 7 hours. The reaction solution was quenched with feed C. Charge D was added and the resulting mixture was stirred at 32 ℃ for 30 minutes. The reaction mixture was partitioned, and the organic layer was collected, washed with brine (15 g) and dried, and neutralized with sodium bicarbonate (0.5 g), neutral alumina (5.0 g) and magnesium sulfate. The resulting organic layer was filtered through filter paper and the solvent was removed under vacuum. The final product was a bright green oil with a% solids of 90+%, Mn of 1430 g/mole and PDI of 1.81, as determined by gel permeation chromatography.

Step 2-hydrophobic polyurethane prepolymer

The following materials were charged in the order described to a suitably equipped reaction flask.

Charge a was added to a suitably equipped reaction flask with stirring. The mixture was heated to 90 ℃ and feed B was added in portions over 20 minutes. The resulting mixture was maintained at 90 ℃ and stirred for 1.5 hours. The reaction mixture was cooled to 80 ℃ and charge C was added. The resulting mixture was kept at 80 ℃ for 1 hour under an air atmosphere and cooled to room temperature. The final product was a bright green slightly viscous solution with a% solids of 50.0, Mn of 2440 and PDI of 1.55 as determined by gel permeation chromatography.

Component N-hydrophobic polyurethane prepolymer

The following materials were charged in the order described to a suitably equipped reaction flask.

(9) The photochromic material E is 3- (4-methoxyphenyl) -3- (4- (2-hydroxyethoxy) phenyl) -6, 11-difluoro-13, 13-dimethyl-3H, 13H-indeno [2',3':3,4] naphtho [1,2-b ] pyran.

Charge a was added to a suitably equipped reaction flask with stirring. The mixture was heated to 90 ℃ and feed B was added in portions over 20 minutes. The resulting mixture was maintained at 90 ℃ and stirred for 1.5 hours. The reaction mixture was cooled to 80 ℃ and charge C was added. The resulting mixture was kept at 80 ℃ for 1 hour under an air atmosphere and cooled to room temperature. The final product was a dark purple slightly viscous solution with a% solids of 45.0.

Component O-hydrophobic polyurethane prepolymer

Step 1

The following materials were charged in the order described to a suitably equipped reaction flask.

Feeding of the feedstock	Material	Weight, g
			A	Photochromic A(5)	112.0
	Trimethylene carbonate	146.0
				Aluminium isopropoxide	3.3
	Chloroform	400(mL)
B	Toluene	200
C	Isocyanatoethyl methacrylate	12.6

Dibutyl tin laurate

4 (drop)

Charge a was charged to a suitably equipped reaction flask. The reaction mixture was stirred under nitrogen for 48 hours. After that, the resulting mixture was washed with dilute hydrochloric acid, 10wt% sodium bicarbonate solution, and dried over magnesium sulfate. After filtration of the magnesium sulfate, the resulting solution was dried under vacuum at 90 ℃ for 1 hour. Charge B was added and the mixture was stirred. Feed C was added and the resulting mixture was held at 76 ℃ for 3 hours under nitrogen atmosphere.

Component P-hydrophobic polyurethane prepolymer

According to the procedure used for the preparation of component O, except that 53.6 g of photochromic A were used instead of 112.0 g.

Component Q-photochromic hydrophobic polyurethane methacrylate

To a 1 liter appropriately equipped reaction flask was added the following materials:

feeding of the feedstock	Material	Weight, g
			A	Photochromic A(5)	26.8
	Trimethylene carbonate	72.0
				Chloroform (Anhydrous)	200(mL)
	Aluminium isopropoxide	1.65
B	Toluene (Anhydrous)	100
C	Dibutyl tin laurate	2 (drop)
				Isocyanate Ethyl methacrylate	6.3

Charge a was added and the reaction flask was purged with nitrogen, sealed with a rubber septum, heated to 35 ℃ with mixing, and held at that temperature for 3.5 hours. The resulting dark purple solution was washed with chloroform (200mL) and hydrochloric acid solution (8 g concentrated HCl in 200 g water). The aqueous phase was separated and removed and the organic phase was washed with 200mL of 10wt% aqueous sodium bicarbonate solution. The resulting organic phase was dried over magnesium sulfate, filtered and added to a rotary evaporation flask. After 1 hour at 90 ℃ rotary evaporation, feed B, a dark purple oil, was added followed by feed C. The resulting mixture was heated to 76 ℃, purged with nitrogen, sealed with a rubber septum, and stirred at 76 ℃ for 3 hours. Thereafter, the reaction mixture was cooled to room temperature and stirred for about 12 hours.

Component R

The following materials were charged in the order described to a suitably equipped reaction flask.

Charge a was added to a suitably equipped reaction flask and the mixture stirred and heated to 90 ℃. After 90 ℃ had been reached, feed B was added in portions over 20 minutes, and after the addition was complete, the resulting mixture was held at 90 ℃ for 1.5 hours. The mixture was cooled to 80 ℃. Feed C was added over 15 minutes and the temperature was maintained at 80 ℃ for 1 hour under an air atmosphere. The% solids was 50.0.

Component S

Following the procedure for the preparation of component R, the following materials were used to produce a final product having 50% solids.

Component T

Following the procedure for the preparation of component R, the following materials were used to produce a final product having 50% solids.

Example 1

The following materials were added in the following order.

The pre-emulsion was prepared by stirring feed a in a glass beaker. The pre-emulsion was sonicated for 10 minutes at room temperature. Passing the pre-emulsion throughM-110P was cycled 8 times at 12,500 psi.M-110P is available from MFICcorporation, Newton, Mass in Microfluidics^TMAnd (4) dividing. Circulation of pre-emulsionNo cooling water was used during the loop. The resulting temperature of the pre-emulsion is about 20-27 ℃. Feed B was added over 10 minutes followed by feed C. The resulting milky violet dispersion was transferred to a rotary evaporation flask and charge D was added. The resulting dispersion was evaporated until no more water was collected and a constant weight was obtained. The solids were determined to be 29.22%,

example 2

Following the procedure of example 1 except that the pre-emulsion was cycled 4 times instead of 8 times, the following materials were used to prepare a milky violet dispersion with a solids level of 30.14%.

Example 3

The procedure of example 1 was followed except that the pre-emulsion was ultrasonically crushed for 5 minutes instead of 10 minutes and circulated 6 times instead of 8 times, and cooling water was added to the external bath to maintain the pre-emulsion temperature at 20-27 ℃. The following materials were used to prepare a milky violet dispersion with a solids level of 31.55% and a water percentage of 9.79%.

Example 4

The procedure of example 1 was followed except that the pre-emulsion was ultrasonically crushed for 5 minutes instead of 10 minutes and circulated 6 times instead of 8 times, and cooling water was added to the external bath to maintain the pre-emulsion temperature at 20-27 ℃. The following materials were used to prepare a milky violet dispersion with a solids level of 33.81% and a water percentage of 3.60%.

Example 5

The following materials were added in the following order.

Feeding of the feedstock	Material	Weight, g
			A	Component F	72.6
	Dimethylethanolamine	1.09
				Acrylic acid butyl ester	13.09
	Component K	167.6

	Toluene	24.2
B	Water (W)	489.5
C	Water (W)	44.0
				Ferric aluminium sulfate	0.009
	Tert-butyl peroxide	0.44
D	Water (W)	71.5
				Sodium metabisulfite	0.55
			E	Propylene glycol	208.0

The pre-emulsion was prepared by: charge a was charged to a narrow neck flask, then stirred, and charge B was added with stirring. The pre-emulsion was sonicated for 5 minutes at room temperature. Passing the pre-emulsion throughM-110P was cycled 6 times at 12,000 psi.M-110P is available from MFIC Corporation, Newton, MA in Microfluidics^TMAnd (4) dividing. The resulting mixture was heated to 35 ℃ and the ingredients of feed C were added with stirring. The ingredients of feed D were added over 10 minutes. After the addition was complete, the resulting mixture was heated to 55 ℃ for 30 minutes. Charge E was added and the resulting milky violet dispersion was transferred to a rotary evaporation flask operating at up to 55 ℃. The resulting dispersion was evaporated until no more water was collected and a constant weight was obtained. The solids were determined to be 36.0% and the water percentage was 1.6.

Example 6

The process of example 5 was followed except that the following materials were used to prepare a milky violet non-aqueous dispersion having a solids level of 35.5% and a water percentage of 2.0.

Feeding of the feedstock	Material	Weight, g
			A	Component F	72.6
	Dimethylethanolamine	1.09
				Acrylic acid butyl ester	13.09
	Component L	143.6
				Toluene	24.2
			B	Water (W)	500.5
			C	Water (W)	44.0
	Ferric aluminium sulfate	0.009

	Tert-butyl peroxide	0.44
D	Water (W)	71.5
				Sodium metabisulfite	0.55
			E	Propylene glycol	209.0

Example 7

The process of example 5 was followed except that the following materials were used to prepare a milky violet non-aqueous dispersion with a solids level of 36.0%.

Feeding of the feedstock	Material	Weight, g
			A	Component F	16.55
	Dimethylethanolamine	0.25
				Acrylic acid butyl ester	2.78
	Component M	34.52
				Toluene	5.5
			B	Water (W)	110.0
			C	Water (W)	10.0
	Ferric aluminium sulfate	0.002
				Tert-butyl peroxide	0.10
			D	Deionized water	16.3
	Sodium metabisulfite	0.125
E	Propylene glycol	45.3

Example 8

The process of example 5 was followed except that the following materials were used to prepare a milky violet non-aqueous dispersion with a solids level of 36.0%.

Feeding of the feedstock	Material	Weight, g
			A	Component F	58.9
	Dimethylethanolamine	0.88
				Acrylic acidButyl ester	13.6
	Component N	121.2
				Toluene	19.6
			B	Water (W)	392.0

C	Water (W)	35.6
				Ferric aluminium sulfate	0.0071
	Tert-butyl peroxide	0.356
D	Water (W)	58.0
				Sodium metabisulfite	0.445
			E	Propylene glycol	175.0

Example 9

The following materials were added in the order described.

The pre-emulsion was prepared by stirring feed a in a glass beaker for 15 minutes. Add pre-emulsion (155.0 g) toM-110P reservoir. After the start of the cycle, feed B was added. The resulting mixture was circulated until the mixture temperature reached 60 ℃, and then cooling water was returned to lower the temperature to 30 ℃. The cycle lasted 15 minutes. Charge C was added over 10 minutes followed by charge D, the resulting milky violet dispersion was transferred to a rotary evaporation flask and charge E was added. The resulting dispersion was evaporated until no more water was collected and a constant weight was obtained. The solids level was determined to be 28.2%.

Example 10

The procedure of example 9 was followed except that 162.7 grams of feed A was fed to the Microfluidizer storage tank and the following materials were used to make the product at a solids level of 28.7%.

Example 11

The procedure of example 9 was followed except that 145.93 grams of feed A were fed to the Microfluidizer storage tank and the following materials were used to make the product, which had a solids level of 30.6%.

Example 12

Following the procedure of example 5, except using the following materials, feed E was added to 144 grams of the product resulting from the addition of feed D to produce a final product having a solids level of 32.8%.

Example 13

The process of example 5 was followed except that the following materials were used and charge E was added to 138 grams of the product resulting from the addition of charge D to produce a final product having a solids level of 34.1%.

Example 14

The process of example 5 was followed except that the following materials were used and charge E was added to 150 grams of the product resulting from the addition of charge D to produce a final product having a solids level of 31.1%.

Comparative example 1

The process of example 5 was followed except that the following materials were used to prepare a milky violet non-aqueous dispersion with a solids level of 30.0%.

Feeding of the feedstock	Material	Weight, g
			A	Component E	15.9
	Dimethylethanolamine	0.47
				Acrylic acid butyl ester	8.0
	Component J	21.5
				Toluene	5.5
			B	Water (W)	115.0
			C	Water (W)	10
	Ferric aluminium sulfate	0.002
				Tert-butyl peroxide	0.10
			D	Water (W)	16.0
	Sodium metabisulfite	0.125
E	Propylene glycol	52.5

Comparative example 2

The following materials were added in the order described.

Feeding of the feedstock	Material	Weight, g
			A	Component H	46.26
	Acrylic acid butyl ester	10.18
				Water (W)	45.12
			B	Component J	22.45
	Methyl isobutyl ketone	16.0
C	Water (W)	30.0
D	Water (W)	12.1
				Ferric aluminium sulfate	0.0013
	Tert-butyl peroxide (70wt% in water)	0.06
E	Water (W)	10.0
				Sodium metabisulfite	0.08

The pre-emulsion was prepared by stirring feed a in a glass beaker. Add pre-emulsion (84.63 g) toM-110T reservoir. After the start of the cycle, feed B was added. The resulting mixture was recycled for 10 minutes. The resulting mixture was charged to an appropriately equipped reaction flask. Feed C was used to rinse the Microfluidizer and added to the reaction flask. Charge D was added to the reaction mixture, followed by charge E over a period of 10 minutes. During the addition of feed E, the temperature of the reaction mixture rose from 19 ℃ to 23 ℃. The resulting milky violet dispersion was transferred to rotary evaporation. The resulting dispersion was evaporated until the solvent and water were removed and a constant weight was obtained. A total of 70 grams of the aqueous dispersion was recovered at a solids level of 39.7% and a pH of 7.88.

Part II-preparation of coating compositions, coated lenses and physical testing thereof

Part A-Melamine coating formulations

The following amounts of material, expressed in grams, were added in the order listed to a one fluid ounce glass jar and mixed thoroughly after each addition to evenly disperse the material. After the addition was complete, each mixture was roller set at the highest scale on a Wheaton bench roller for a minimum of 4 hours at room temperature.

TABLE 1 formulations of examples 1A, 2A, 3B, 3C and 4A

(10) Reported as ureidopropyltriethoxysilane, available from Gelest.

(11) Reported as melamine formaldehyde, commercially available from Cytec.

(12) Reported as barrier amine light stabilizers, available from Ciba Specialty Chemicals.

Application of part B-coating

Directly using a diameter of 76 mmCoatedPolycarbonate flat lenses. The lenses of examples 1A, 2A, 3B, 3C and 4A were treated with oxygen plasma at an oxygen flow rate of 100 milliliters (mL)/minute at 100 watts power for one minute. The lenses were coated with the solutions of examples 1A, 2A, 3B, 3C and 4A by a spin coating method. About 1-2mL of each example solution was dispensed onto the lens and the lens was spun at 765rpm for 8 seconds. The coated lenses were cured in an intensive oven by the following cure cycle: 80 ℃ 5 minClock and 140 ℃ for 1 hour, and cooling to room temperature. Treating the coated lens with said oxygen plasma and using by spin coating1080 coating solution (commercially available sol gel hard coat preparation coating solution from PPG Industries, Inc.). About 1-2mL of HI-GARD 1080 were dispensed onto the lenses and the lenses were spun at 1067rpm for 8 seconds. Then, make the coating coated1080 the lenses coated with the solution were cured at 120 ℃ for 3 hours. Additional lenses coated with example 1A were uncoated1080, which was designated example 1B and tested for resistance to caustic as described below. The lenses of examples 1A, 2A and 4A were subjected to the photochromic test described in section III.

Part C-physical testing

The coated lenses prepared in part B were tested for primary and secondary adhesion. The lenses coated with examples 3C and 4A were tested for haze and the lens designated example 1B was tested for resistance to caustic solution.

The primary and secondary bond tests were conducted using a modified ASTM D-3539 standard test method for measuring bond by tape test-method B. The standard method was modified to include retesting at different locations on the same sample tested for primary bonding after holding the sample in boiling water for 30 minutes, followed by a secondary bonding test. Results are reported as% residue after testing. The tape used was 3M #600 scotch tape or TESA 4651 tape. All lenses showed 100% residue as a result.

Haze testing was performed on the coated lenses of examples 3C and 4A. The haze of each lens was measured after 30 minutes soaking in deionized boiling water. The lenses were wiped dry and cooled to room temperature before testing. Haze was measured using a Hunter Lab UltraScan XE instrument. The haze of the lens coated with example 3C was 0.92 and the haze of the lens coated with example 4A was 25.9. Lower amounts of haze, expressed as lower numbers, are desirable results.

Caustic testing was performed on lenses coated with the solution of example 1B. The lenses were soaked in a caustic solution of 15 wt% sodium hydroxide, 5 wt% Dowanol PM and 80 wt% deionized water and heated to 60 ℃ in an ultrasonic water bath. After removal of the lens, it was rinsed with deionized water and checked for any coating loss. Coating loss greater than 5.0mm from the edge of the lens was considered a failure. The lens coated with the solution of example 1B passed the test.

Part D-solvent compatibility test

The materials of example 5 and comparative example 1 were tested for compatibility and determined by visual inspection in various solvents as follows. The materials of example 5(0.5 g) and comparative example-1 (0.5 g) were each added to a series of 20mL glass vials. The following different solvents were added to each vial in amounts of 10 grams each. The results listed in Table 2 below were determined immediately upon addition and scored on a 1-5 basis based on solubility. A score of 1 corresponds to a very poor dissolution response, e.g. silver chloride in water, while a score of 5 corresponds to soluble, i.e. fully miscible.

TABLE 2 solvent compatibility of example 5 and comparative example 1

Solvent(s)	Example 5	Comparative example 1
			2-heptanone	5	1
Acetone (II)	3	1
			Ethyl acetate	3	1
3-Ethoxypropionic acid ethyl ester	5	1
			1-methoxy-2-propanol	5	5
Xylene	1	1

Partial E-polyurethane coating formulations

Step 1-preparation of acrylic polyol

The following materials were added in the order described.

(13) Reported as propylene glycol methyl ether, available from the Dow Chemical Company.

Feed a was charged to a 1 gallon stainless steel pressure reactor with stirring and the reactor was heated to 99 ℃ at atmospheric pressure. After reaching 99 ℃, the reactor was sealed and further heated to 165 ℃. When the reactor reached 165 ℃ at 39psi, feeds B and C were added over 3 hours. Feed B and C were completed and feed D was added over 1 hour when 62psi reached 165 ℃. After the addition of feed D at atmospheric pressure was complete, the reactor temperature was maintained at 165 ℃ for 1 hour. The reaction mixture was cooled to 90 ℃ and poured through a 10 μm filter bag. The reaction yielded 3,500 grams of resin with a solids content of 78.5%.

Step 2 preparation of polyurethane coating compositions A and B

Coating composition A

The following materials were added in the order described with mixing.

(14) Reported as polyether modified polydimethylsiloxane, available from BYK USA.

(15) HALS-1 is phenyl (3, 5-di-tert-butyl-4-hydroxy-benzyl) -malonic acid-bis (l,2,2,6, 6-tetramethyl-4-piperidinyl) ester, prepared as described in U.S. patent 4,198,334, column 14, line 59 to column 21, line 29, the disclosure of which is incorporated herein by reference.

(16) Reported as sterically hindered phenolic antioxidants, which are commercially available from Ciba specialty chemicals.

(17) Reported as 3, 5-dimethylpyrazole-terminated IPDI-type isocyanates, available from Baxenden Chemicals Limited.

Coating composition B

The following materials were added in the order described with mixing.

(18) Reported as gamma-ureidopropyltrialkoxysilane in methanol, available from GESilicones-OSi Specialties.

Application of partial F-polyurethane coating

Coated with a diameter of 70 mmIs/are as followsThe polycarbonate flat lens was used as it is. The lenses coated with the fluorine-coating compositions a containing examples 6,7 and 8 and the lenses coated with the fluorine-coating compositions B containing examples 12,13 and 14 were subjected to corona treatment in a 3DT MultiDyne 1 system, wherein each lens was placed under a corona source rotating at about 200rpm for about 1 inch (2.54cm) for about 3-4 seconds. The lenses were coated with solutions of coating compositions a and B by spin coating. Approximately 1-2mL of each example solution was dispensed onto the lens and the lens was spun at 1,400rpm for 5 seconds and then 2,000rpm for 1 second. The coated lenses were cured in an intensive oven at 125 ℃ for 1 hour and cooled to room temperature. The lenses were soaked for the photochromic test described in section III.

Part G-UV curable acrylic coating composition

The following materials were added in the order stated

(19) Reported as propoxylated neopentyl glycol diacrylate, available from SARTOMER.

(20) Reported as a hexafunctional aliphatic urethane acrylate available from cyteicindustries Inc.

(21) Reported as tetrafunctional aliphatic urethane acrylates, available from cyteicnds Inc.

(22) Reported as n-methylaminopropyltrimethoxysilane, available from GELEST Inc.

(23) Reported as dipropylene glycol dimethyl ether, available from Dow Chemical Inc.

(24) NMP was N-methylpyrrolidinone (Biotech grade) available from Aldrich chemical.

Charge a was added to a suitable vessel equipped with a stirrer and mixed. Charge B was added and the resulting mixture was stirred for 2-5 minutes. Charge C was added and the mixture was heated to 60 ℃ and mixed until all material was dissolved. The stirring was stopped and the mixture was held at 60 ℃ for 30-60 minutes. After cooling to room temperature, lenses as described in section H were coated with each coating solution.

Partial H-coating application

The lenses prepared in part G were heated in an intensive oven at an oven temperature of 80 ℃ for 15 minutes and then the solutions of examples 9A and 9B were applied by spin coating. Approximately 1-2mL of each example solution was dispensed onto the lenses and the lenses designated 9A-1 and 9B-1 were spun at 1,400rpm for 7 seconds and the lenses designated 9A-2 and 9B-2 were spun at 1,400rpm for 10 seconds. The coated lenses were placed in an EYE UV curing machine using two V-bulbs (160W/m)²) Curing was done at a speed of 5ft/min (152.4 cm/min). After the lenses were cured, they were retreated with the corona source described in section G, after which a proprietary silane based sol gel hardcoat was applied to each lens at a speed of 1,400rpm for 12 seconds. The coated lenses were then cured in a power oven at 105 ℃ for 3 hours. The lenses were soaked for the photochromic test described in section III.

Part I-preparation of coating compositions with commercially available Sol-gel products

The following materials in the amounts expressed in grams were added to a suitable container in the order described. After charge B was added to charge a, the vessel was shaken for a minimum of 5 seconds to ensure adequate mixing of the coating solution. Thereafter, the solution was left to stand for a minimum of 10 minutes to allow any foam formed to dissipate.

TABLE 3 formulation of coating compositions 10A, 10B, CE-2A and CE-2B

(25) Reported as a sol gel hard coating solution, available from PPG Industries, Inc.

The coatings of comparative examples 2A and 2B were flocculated within minutes after preparation of the coating solutions in table 2. Part B procedure-after application of the coatings, the coatings of examples 10A and 10B were applied to the lenses except that, prior to coating, the lenses were treated with oxygen plasma at 120 Watts for 3 minutes instead of 100 Watts for 1 minute; the lens coated with the solution of example 10A was coated at 463rpm instead of 765 rpm; the coated lenses were dried at 80 ℃ for 10 minutes instead of 5 minutes; and without coating the next1080 coating the solution. The primary and secondary adhesion tests performed on the coated lenses are described in part C-physical testing. As a result, both groups of lenses exhibited 100% residue in the primary and secondary adhesion tests. The lenses were soaked for the photochromic test described in section III.

Preparation of part J-coating composition with commercially available Hi-Index Sol-gel product

Following the procedure of part I, the materials listed in table 4 were used to form coating compositions, 11A, 11B and 11C, containing only the control (part J) of the commercial product.

TABLE 4-control and formulations of examples 11A, 11B and 11C

(26) High index sol gel hard coating solutions are reported and are available from PPG industries, Inc.

The coating solution was applied to the lenses as described in section J, except that the rotation rates were as follows: control (part J) 463 rpm; 11A is 493 rpm; 11B was 614 rpm; and 11C at 704 rpm. The solids content of example 11, based on total solids weight, 11A in the coating solution was 10.7%; 21.6% in 11B; and 42.3% in 11C. The refractive index was measured for each coated lens as described in Polarized LightMicroScopy (Walter C. McCrone et al, page 126, Tenth Printing, 1997, copyright 1984, McCrone Research Institute, 2820South Mich mirror, Chicago, IL 60616-.

The abrasion resistance of the lenses coated with the solutions of controls, 11A, 11B and 11C was determined using the ASTM F735-81 standard test method by the oscillating sand method for abrasion resistance of clear plastics and coatings. The test specimens were exposed to 300 oscillations in an ASTM test method using 500 grams of alundum. The Bayer Abrasion Resistance Index (BARI) of the individual samples listed in Table 1 was calculated by dividing the% haze of the uncoated test sample divided by the% haze of the coated test sampleHomopolymer preparation of the monomers. The resulting numbers are coated test specimens andan indication of how high the uncoated test sample made from the monomer is compared to the abrasion resistance. Haze and projection BYK before and after abrasion testPlus instrument measurement. The refractive index of the coated lenses and the BARI results are shown in Table 5.

TABLE 5 refractive index and BARI of lenses coated with controls, 11A, 11B, and 11C

Class of coating	Refractive index	BARI
			Control (part J)	1.578	4.6
11A	1.572	2.4
			11B	1.562	1.4
11C	1.548	1.1

Preparation of coating compositions with part K-commercially available Sol-gel products

The materials listed in table 6 were used to form coating compositions containing only commercial product controls (part K), 10C, 10B, 10D, 10E, 10F, 10G, 10H, 10I, following the procedure of part I.

TABLE 6-coating composition formulations for controls (part K), 10C, 10D, 10E, 10F, 10G, 10H, and 10I

The procedure for applying the coating solution to the lens was followed as described in section J except that the rotation rates were as set forth in table 7.

TABLE 7 rotational speed of applied coating

Class of coating	Rotational speed (rpm)
		Control (part K)	1067
10C	463
		10D	463
10E	553
		10F	614
10G	674
		10H	765
10I	1187

The coated lenses were subjected to the primary and secondary adhesion tests described in part C-physical testing. As a result, all lenses exhibited 100% residue for the primary and secondary adhesion tests. The bayer abrasion resistance index was determined as described in section J, and the results, as well as the initial haze measurements, are listed in table 8 below.

TABLE 8 BARI and initial haze results

Class of coating	Initial haze	BARI
			Control (part K)	0.15%	5.2
10C	0.14%	3.1
			10D	0.16%	2.5
10E	0.14%	1.8
			10F	0.16%	1.6
10G	0.15%	1.4
			10H	0.14%	1.2
10I	0.17%	0.9

Optical dichroism Performance testing of partially III-coated lenses

The photochromic properties of the coated lenses listed in table 9 were determined as follows. The coated lenses prepared in part II were tested for photochromic response on a Bench of Bench scale for Measuring photochromic ("BMP") manufactured by esilor, ltd. The optical bench was held at a constant temperature of 23 ℃ (73.4 ° F) during testing.

Each coated lens was exposed to 365-nm ultraviolet light for about 10 minutes at a distance of about 14 cm to activate the photochromic material prior to testing on the optical bench. By LicoThe radiation intensity of UVA (315-². The lens was then placed under a 500 watt high intensity halogen lamp for about 10 minutes at a distance of about 36 centimeters to decolorize (deactivate) the photochromic material. The lens illuminance was measured with a Licor radiation spectrometer and found to be 21.4 Klux. The lenses were kept in a dark environment at room temperature (21 ℃ to 24 ℃, or 70 ° F to 75 ° F) for at least 1 hour and then tested on an optical bench. The UV absorbance of the lens at 390 and 405nm was measured before the bench measurements.

The BMP optical bench has two 150W optical modules at right angles to each otherXenon arc lamp model # 66057. The light path of the lamp 1 passes 3mmKG-2 bandpass filters and appropriate neutral density filters for the desired UV and partial visible radiance levels. The light path of the lamp 2 passes through 3mmKG-2 band-pass filter,The segmented band 400nm cutoff filter and a suitable neutral density filter guide to provide supplemental visible light illumination. A 5.1cm x 5.1cm (2 inch x 2 inch) 50% polka spot array beam splitter at 45 ° to each lamp was used to mix the two beams. A combination of neutral density filters and voltage control of the xenon arc lamp is used to adjust the intensity of the irradiance. Specialized software was used for BMP to control time intervals, irradiance, air vent (air cell) and sample temperature, shutters, filter selection and response measurement. With optical fibre cables for transmitting light through the lensMCS 501 type spectrophotometer was used for response and color measurements. Photopic response of lenses containing mixtures of photochromic materials in compositions A and BMeasurement, response measurements at 565-570nm were performed on the remaining portion of the lens containing photochromic A.

The power output of the optical bench, i.e. the dose of light to which the lens is exposed, was adjusted to 6.7 watts/m²(W/m²) UVA, integrated from 315-380nm and 50Klux illumination, and integrated from 380-780 nm. The measurement of the power output was performed using an optometer and software contained in the BMP.

Response measurements, expressed as the change in optical density (Δ OD) from the unactivated or decolored state to the activated or colored state, were determined by: an initial non-activated light transmittance is established, the grating of the xenon lamp is turned on, and the light transmittance is measured by activation at selected time intervals. The change in optical density is determined according to the following formula: Δ OD = log₁₀(% Tb/% Ta), where% Tb is the% transmittance in the bleached state and% Ta is the% transmittance in the activated state.

The results of this test are shown in table 9 below, where the coated lens has an absorbance at 390nm and a first fade half-life ("T1/2") value, which is the time interval in seconds after the activating light source is removed for the delta OD of the activated form of photochromic material in the coating to reach half the fifteen minute delta OD at 23 ℃ (73.4 ° F). The second fade half-life ("2T1/2") value is the time interval in seconds for the delta OD of the activated form of the photochromic material in the coating to reach one-quarter of the delta OD in fifteen minutes at 23 ℃ (73.4 ° F). The third fade half-life ("3T1/2") value is the time interval in seconds at which the Δ OD of the activated form of the photochromic material in the coating reaches one-eighth of the Δ OD in fifteen minutes at 23 ℃ (73.4 ° F).

TABLE 9 photochromic response results

The invention has been described with reference to specific details of particular embodiments thereof. It is not intended that such details be regarded as limitations upon the scope of the invention except insofar as and to the extent that they are included in the accompanying claims.

Claims (33)

1. A non-aqueous dispersion of photopolymer microparticles comprising:

a) an organic continuous phase comprising an organic solvent; and

b) photosensitive polymeric microparticles dispersed in the organic continuous phase, wherein the microparticles comprise an at least partially polymerized component having an integrated surface region and an interior region, wherein the surface region comprises a polymeric material that is soluble in the organic solvent, the interior region comprises a polymeric material that is insoluble in the organic solvent, and the surface region and/or interior region is photosensitive.

2. The non-aqueous dispersion of claim 1, wherein the organic solvent is a polar solvent comprising an alcohol, an ether, an amide, a nitrile, an ester, a ketone, and/or a lactam.

3. The non-aqueous dispersion of claim 2, wherein the alcohol is a diol.

4. The non-aqueous dispersion of claim 2, wherein the alcohol is ethylene glycol.

5. The non-aqueous dispersion of claim 1, wherein the photosensitive material is substantially non-extractable from the photosensitive polymer microparticles.

6. The non-aqueous dispersion of claim 1, wherein the photopolymer microparticles are magnetic, magnetically responsive, electrically conductive, dichroic, chromophoric, and/or chemically reactive with a crosslinking material.

7. The non-aqueous dispersion of claim 1, further comprising a nanopigment and/or a non-photosensitizing dye.

8. A method of making a non-aqueous dispersion of photosensitive microparticles comprising:

a) preparing an aqueous dispersion of a photosensitive material and a polymerizable component, wherein the polymerizable component comprises at least one hydrophilic functional group and at least one hydrophobic functional group;

b) subjecting the dispersion of a) to conditions sufficient to form microparticles;

c) at least partially polymerizing the polymerizable component;

d) combining the dispersion with an organic continuous phase comprising an organic solvent; and

e) removing water from the dispersion such that the final water content of the non-aqueous dispersion is less than 30 weight percent; wherein e) is performed before or after d).

9. The method of claim 8, wherein the organic solvent is a polar solvent comprising an alcohol, an ether, an amide, a nitrile, an ester, a ketone, and/or a lactam.

10. The method of claim 9, wherein the alcohol is a diol.

11. The method of claim 9, wherein the alcohol is ethylene glycol.

12. The method of claim 8, wherein the hydrophilic functional groups are provided by substantially hydrophilic monomers and the hydrophobic functional groups are provided by substantially hydrophobic monomers, wherein the substantially hydrophobic monomers exhibit a hydrophilic-lipophilic balance number of less than 10 and the substantially hydrophilic monomers exhibit a hydrophilic-lipophilic balance number of greater than 10.

13. The method of claim 12, wherein the substantially hydrophilic monomer is prepared from a triisocyanate and/or a polycarbonate-functional diol prepared from the reaction of 1, 6-hexanediol with phosgene or dimethyl carbonate.

14. The method of claim 12, wherein the polymerizable component further comprises at least one copolymerizable material different from the substantially hydrophilic monomer or different from the substantially hydrophobic monomer.

15. The method of claim 8, wherein b) comprises subjecting the dispersion of a) to high shear stress conditions.

16. A method of making a non-aqueous dispersion of photosensitive microparticles comprising:

a) preparing an aqueous dispersion of a substantially hydrophilic prepolymer component;

b) preparing an aqueous dispersion of a substantially hydrophobic prepolymer component, wherein the dispersion of a) and/or b) further comprises a photosensitive material;

c) combining the dispersions of a) and b) to form a mixture and subjecting the mixture to conditions sufficient to form microparticles;

d) polymerizing the prepolymer component of the mixture;

e) combining the mixture with an organic continuous phase comprising an organic solvent; and

f) removing water from the mixture such that the final water content is less than 30 wt%; wherein f) is carried out before or after e),

wherein the substantially hydrophobic prepolymer component exhibits a hydrophilic-lipophilic balance number of less than 10 and the substantially hydrophilic prepolymer component exhibits a hydrophilic-lipophilic balance number of greater than 10.

17. The method of claim 16, wherein the photosensitive material is an organic photochromic material having at least one functional group capable of polymerizing with the prepolymer component of a) and/or b).

18. The method of claim 16, wherein step c) comprises subjecting the mixture to high shear stress conditions.

19. The method of claim 16, wherein the photosensitive material is selected from the group consisting of fluorescent materials, phosphorescent materials, nonlinear optical materials, photochromic materials, or mixtures thereof.

20. The method of claim 16, wherein the organic solvent is a polar solvent comprising an alcohol, an ether, an amide, a nitrile, an ester, a ketone, and/or a lactam.

21. The method of claim 20, wherein the alcohol is a diol.

22. The method of claim 20, wherein the alcohol is ethylene glycol.

23. A curable, photosensitive film-forming composition prepared from:

(a) a film-forming component comprising at least one material having reactive functional groups; and

(b) a non-aqueous dispersion of photosensitive polymeric microparticles comprising:

i) an organic continuous phase comprising an organic solvent; and

ii) photosensitive polymeric microparticles dispersed in the organic continuous phase, wherein the microparticles comprise an at least partially polymerized component having an integrated surface region and an interior region, wherein the surface region comprises at least one substantially hydrophilic region, the interior region comprises at least one substantially hydrophobic region, and the surface region and/or interior region is photosensitive, wherein the substantially hydrophobic region exhibits a hydrophilic-lipophilic balance number of less than 10 and the substantially hydrophilic region exhibits a hydrophilic-lipophilic balance number of greater than 10.

24. The film-forming composition of claim 23, wherein the film-forming component (a) comprises the formula R_xM(OR')_z-xWherein R is an organic group, M is silicon, aluminum, titanium, and/or zirconium, each R' is independently an alkyl group, z is the valence of M, and x is a number less than z.

25. The film-forming composition of claim 23, wherein the organic solvent is a polar solvent comprising an alcohol, an ether, an amide, a nitrile, an ester, a ketone, and/or a lactam.

26. The film-forming composition of claim 25, wherein the alcohol is a diol.

27. The film-forming composition of claim 25, wherein the alcohol is ethylene glycol.

28. A substrate coated with the curable film-forming composition of claim 23.

29. The coated substrate of claim 28, wherein the substrate is an ophthalmic element selected from the group consisting of corrective lenses, non-corrective lenses, contact lenses, intraocular lenses, magnifying lenses, protective lenses, and visors, and wherein the refractive index of the film-forming composition, after curing, is greater than 1.5.

30. The film-forming composition of claim 23, wherein the material having reactive functional groups in film-forming component (a) comprises an aminoplast, a blocked or free polyisocyanate, and/or an ethylenically unsaturated compound.

31. The film-forming composition of claim 30, wherein the material having reactive functional groups in film-forming component (a) comprises an aminoplast, and wherein the substantially hydrophilic region of the surface region of the microparticles is prepared from an isocyanurate, wherein said substantially hydrophilic region exhibits a hydrophiiic-lipophilic balance number greater than 10.

32. The film-forming composition of claim 23, wherein the photopolymer microparticles contain functional groups that are reactive with the reactive functional groups in the material in the film-forming component (a).

33. The film-forming composition of claim 23, wherein the photopolymer microparticles are photochromic.