Photochromic article comprising dendritic polymeric acrylate

(Citation of related application) This application claims priority to provisional patent application number 60 / 712,946 filed on August 31, 2005. This provisional patent application is incorporated herein by reference.

(Field of invention) The present invention relates to novel photochromic coatings and articles to which such photochromic coatings are applied. More specifically, the present invention relates to an optical article having such a photochromic coating on the surface of the article (eg, an ophthalmic article such as an ophthalmic lens).

(Background of invention) Photochromic articles are prepared by incorporating a photochromic material within the article. This is achieved by mixing the photochromic material into one or more precursors of the article, for example incorporating the photochromic material into a polymerizable composition used to prepare the article. Another proposed approach is to allow the photochromic material to be absorbed into and under the surface of the article by conventional swelling methods (eg, thermophoresis). Such articles physically change from their normal colorless form to a colored form when the photochromic material (eg, an organic photochromic material) is exposed to chemical rays, and return to their original colorless form when the chemical rays are removed. Has been reported to have sufficient free volume in the article.

However, there are some materials to which the above method cannot be applied. It has been reported that such materials do not have sufficient free volume in the matrix or body of the material (eg, in the region just below the surface of the material) to apply the material for commercial photochromic applications. Has been done. Such materials include conventional glass (related to organic photochromic materials); thermoplastic polymers (eg, polyol (allyl carbonate) monomers, especially allyl diglycol carbonate monomers (eg, diethylene glycol bis (allyl carbonate))). (Prepared from materials), and their copolymers; thermoplastic polymers with high glass transition temperatures (eg, commonly known thermoplastic bisphenol A-based polycarbonates); highly crosslinked optical polymers; and others. Such polymeric materials are included. In order to enable the use of such materials in photochromic applications, it has been proposed to apply photochromic coatings (eg, organic coatings) on their surfaces.

Depending on the application, it may be economically preferable to use a radiation curable coating composition containing a photochromic substance. These coating compositions are applied to the surface of the non-photochromic receptive material of choice and are cured, for example, by irradiation with ultraviolet light. Radiation curable coating compositions usually include a photoinitiator that initiates the curing mechanism. In general, photoinitiator compounds have an aromatic ring in their structure and effectively absorb ultraviolet light. In addition, these compounds are usually of low molecular weight to improve solubility in radiation curable compositions, resulting in relatively volatile when exposed to heat. These properties can cause yellowing of the cured composition when the curable coating composition containing the photoinitiator and the cured coating composition are exposed to heat and light during and after curing, respectively. , And can produce an unpleasant odor. Furthermore, it is also known that unreacted photoinitiators may remain in the cured coating composition after curing and may seep out of the coating.

<p num="0006"> Thus, for example, a photochromic-containing coating composition that does not require a photoinitiator for curing or requires less photoinitiator than is commonly used in curing a radiation curable coating composition. For example, it is desirable to utilize a radiation curable coating composition). Further, it would be desirable to utilize such a coating composition as a photochromic coating of a material that is not receptive to incorporating the photochromic material within the material matrix (core) or subsurface region.</p>

<p num="0007"> (Simple gist of the invention) In a non-limiting embodiment of the invention, (a) a hard substrate having at least one surface suitable for adaptation to a photochromic coating, and (b) on at least a portion of the surface of the hard substrate. Articles are provided that include a transparent photochromic coating comprising a dendritic polymeric acrylate, comprising a transparent photochromic coating comprising at least one photochromic material in a photochromic amount.</p><p num="0008"> In another non-limiting embodiment, (a) an optical hard substrate having at least one surface that can be adapted to a photochromic coating, and (b) on at least a portion of the surface of the optical hard substrate. An optical article comprising a transparent photochromic coating comprising a dendritic polyester acrylate and comprising a photochromic amount of at least one photochromic material (eg, an organic photochromic material). In one non-limiting embodiment, the optical article is an eye article, such as a lens.</p><p num="0009"> In a further non-limiting embodiment of the present invention, the photochromic ophthalmic article further comprises an abrasion resistant coating (eg, a hard coating containing an organosilane) on top of the photochromic coating.</p>

(Detailed description of the invention) In the present specification (excluding operation examples), unless otherwise specified, all numbers representing the amounts and ranges of components that can be used in the following description and claims, reaction conditions, etc. are referred to as "in all examples". It shall be understood that it is modified by the term "about". Therefore, unless otherwise indicated, the numerical parameters described in the present specification and the appended claims are approximate values, and these approximate values are the results obtained by the process of the present invention and the present invention. It may vary depending on the result of the properties sought in the article of the invention. At least, and without attempting to limit the application of the doctrine of equivalents to the appended claims, each numerical parameter takes into account the reported number of valid digits and is at least interpreted by applying the usual rounding method. It must be. In addition, the articles "a," "an," "said," and "the" used in this specification and the appended claims are plural unless explicitly and explicitly limited to one referent. It is intended to include referents as well.

Although the numerical ranges and numerical parameters that describe the broad scope of the present invention are approximate values, the numerical values described in the particular examples are reported as accurately as possible. However, each number inherently contains some error that inevitably arises from the standard deviation seen in each test measurement. It should also be understood that any numerical range listed herein is intended to include a subrange contained therein. For example, the range "1-10" is a partial range between the stated minimum value 1 and the stated maximum value 10; that is, a range containing a minimum value of 1 or more or a maximum value of 10 or less. Intended to include. Since the disclosed range is continuous, it includes all values between the minimum and maximum values. Unless otherwise specified, the various numbers specified in this application are approximations as described.

The following terms, as used in the following description and claims, have the following meanings: The terms "acrylic" and "acrylate" are used interchangeably (unless their intended meaning is changed by interchangeable use) and unless otherwise stated, acrylic acid, lower alkyl substituted acrylic acid. (For example, C such as methacrylic acid and etacrylic acid₁~ C₅Substituted acrylic acids), and their Cs such as derivatives of acrylic acids (eg, methyl acrylates, methyl methacrylates, etc.)₁~ C₅Alkyl esters) are intended to be included. For example, the term "(meth) acrylic" or "(meth) acrylate" used in connection with the term "(meth) acrylate monomer" refers to the acrylic / acrylate form and methacrylic of the material described (eg, monomeric material). Intended to include both / methacrylate forms.

The terms "cured", "cured" or similar used in connection with a cured or curable composition (eg, "cured composition" in a particular description) form a curable composition. It is intended to mean that at least a portion of the polymerizable and / or crosslinkable component to be polymerized and / or crosslinked at least partially. In non-limiting embodiments, the crosslink density can range from 5% to 100% of complete crosslinks. In alternative non-limiting embodiments, this crosslink density can range from 35% to 85% of total crosslinks, eg, 50% to 85%. This crosslink density can range between any combination of the above values (including the listed values).

The terms "on top", "added", "attached", "bonded", "bonded" or similar have the terms described material (eg, coating, film or layer) directly bonded to the desired surface. It means that it is (superimposed) or indirectly bonded to the surface of the object via one or more other coatings, films or layers.

The term "eye" refers to elements and articles related to the eye and vision, including, but not limited to, spectacle lenses (eg, corrective lenses, non-corrective lenses, and magnifying lenses).

For example, the term "hard" used in connection with a substrate for a photochromic article means that the designated article is self-standing.

The terms "optical", "optical coating" or similar to the effect indicate that the specified substrate, article, material or coating exhibits a light transmission value of at least 4% (transmitting incident light), eg Haze Gard Plus measurements. It means that the haze value of less than 1% (for example, the haze value of less than 0.5%) is exhibited when measured by the device at a wavelength of 550 nm. The optical base material includes, but is not limited to, a colored base material, a photochromic base material, a polarizing base material, a colored photochromic base material, and a colored polarized light base material.

For example, the term "base material" used in connection with the term hard base material means an article having at least one surface that can be adapted to a photochromic coating (eg, a photochromic polymer coating). That is, the substrate has a surface to which a photochromic coating can be applied. Non-limiting embodiments of the shape that such a substrate surface may have include, but are limited to, convex and / or concave as exemplified by the various base curves used in ocular lenses. Includes non-round, flat, tubular, spherical, flat, substantially flat, flat and / or plano-convex, curved.

For example, the term "coloring" used in connection with eye articles, coatings, films and substrates means that the described material comprises a fixed light emission absorber on or within the described material. To do. Non-limiting embodiments of fixed light emission absorbers include, but are not limited to, conventional color dyes, infrared and ultraviolet absorbing materials. The coloring material has a visible light absorption spectrum that does not change much in response to chemical rays.

The term "chemical ray" includes both visible and ultraviolet light.

For example, the term "matching" used in connection with the case where a photochromic coating is compatible with an abrasion resistant coating is a wear resistant coating (a wear resistant coating applied directly on the surface of a cured photochromic coating). For example, an organosilane-containing hard cord) can have an abrasion resistant coating that adheres to a surface that is applied under normal handling / abrasion conditions as measured by conventional crosshatch tape peeling adhesion tests. And / or the wear resistant coating means that it does not cause crazing after application and curing.

The term "dichroic material", "dichroic dye" or similar term means a material / dye that absorbs one of the two ov-plane polarized components of transmitted light more than the other. Non-limiting embodiments of bicolor materials / dyes include indigoids, thioindigoides, merocyanines, indans, azo dyes and poly (azo) dyes, benzoquinones, naphthoquinones, anthraquinones, (poly) anthraquinones, anthrapyrimidineones, iodine, And iodates are included.

For example, the term "transparent" used in connection with substrates, films and / or coatings allows the described substrates, coatings and / or films to transmit light without scattering light so clearly that it is perceptible. It means that it has the property of being able to clearly see what is on the other side.

The term "dendrimer" or "dendritic polymer" means a three-dimensional polymer having a multivalent core that covalently binds to at least two regular dendritic (dendritic) branches that extend over at least two generations. Each dendritic branch (or generation) extends from the core or the generation of the previous branch, and each branch of each generation has the same number of reaction sites, and the next generation of branches (exists) from that reaction site. If) spreads, or its reaction site acts as the terminal reaction site of the last generation of its bifurcation. The dendrimer may be symmetrical or asymmetric. The term "dendrimer" includes dendrons and hyperbranched molecules.

The term "dendrimer" refers to a type of dendrimer having a branch starting from the core, which is the core, or a branch starting from the center that can be attached to the core either directly or through a connecting portion. ..

The term "dendritic polymer acrylate" means a dendrimer (or dendritic polymer) modified to have a terminal acrylic reaction site. The number of terminal acrylate groups in dendritic polymers can vary over a wide range. In alternative non-limiting embodiments, the proportion of terminal acrylic groups ranges from 5 to 100%, eg, 20 to 90%, or 40 to 80, relative to the initial number of terminal reaction sites on the dendritic polymer. It can be in the range of% (eg 45-80%).

The term "dendritic polyester acrylate" (or a term to the same effect) is a viscosity reducing material having a group that is acrylicized by or during the acrylicization procedure of dendritic polyester macromolecules (eg, 1). It means a composition produced by acrylicizing a dendritic polyester type macromolecule containing one or more alcohols having one or more hydroxyl groups.

The term "dendritic polyester acrylate coating" (or a term to the same effect) refers to a coating produced by curing a composition comprising a dendritic polyester acrylate.

The term "composition comprising a dendritic polyester acrylate" (or a term to the same effect) refers to a dendritic polyester acrylate (or a mixture of multiple dendritic polyester acrylates) and, optionally, at least one other radiation. It means a composition containing a curable material or a thermosetting material (for example, a mixed composition of a dendritic polyester acrylate and a radiation curable and / or a thermosetting acrylic material (for example, a (meth) acrylic monomer)). In addition, auxiliary materials normally included in coating compositions may be included in compositions containing dendritic polyester acrylates.

Photochromism is a phenomenon associated with reversible color changes in photochromic organic or photochromic inorganic materials (eg, chromen or silver halides), or articles containing such materials. Exposure to activated UV and other sources of chemical radiation changes the color of the photochromic material, for example to a darker color. When the activated radiation is removed or the radiation is discontinued, the photochromic material returns to its original color or colorless state.

It is considered to be the cause of the reversible color change (for example, the change in the absorption spectrum with respect to the electromagnetic spectrum of visible light (generally described as the range of 400 to 700 nm)) characteristic of various organic photochromic compounds. The mechanism to be used has already been described. See, for example, John C. Crano, "Chromogenic Materials (Photochromic)", Kirk-Othmer Encyclopedia of Chemical Technology, 4th Edition, 1993, pp.321-332. Cyclic electron mechanisms are believed to be involved in the mechanism responsible for the reversible color changes of organic photochromic compounds (eg, indolinospiropyran, indolinospiroxazine, and naphthopyran). Upon exposure to activated UV light, these organic photochromic compounds transform from a colorless ring-closed form to a colored ring-opened form.

According to a non-limiting embodiment of the present invention, there is provided a transparent photochromic coating containing a dendritic polymeric acrylate that can be applied to the surface of a hard substrate (eg, an optically rigid substrate). Dendrimers have already been described in the field of polymer technology. Such a material can be modified to contain a terminally reactive acrylic group, for example by reaction with an acrylicizing agent, and such a dendritic polymer acrylate is the transparent photochromic coating of the present invention. Can be used for preparation. Non-limiting examples of dendritic polymeric acrylates include epoxide-amine dendrimers, carbosilane dendrimers, amidoamine dendrimers, polysulfide dendrimers, polysiloxane dendrimers, polyaminosulfide dendrimers, polyether dendrimers, polythioether dendrimers, polyester dendrimers, polyesteramides. Includes acrylate-modified dendrimers selected from dendrimers, poly (ether ketone) dendrimers and the like.

In a non-limiting embodiment, the dendrimer is an amide amino polymer, which is referred to as a polyamide amine high density star polymer. See, for example, US Pat. No. 4,558,120. Such a dendrimer can be represented by the formulas listed in column 7, lines 10-15 of '120. A description of such a dendrimer and its preparation method is described in column 2, line 39 to column 9, line 18 of No. 120, which is incorporated herein by reference. ing.

In a further non-limiting embodiment, the dendrimer is an epoxide amine polymer. Such a dendrimer has (a) a reaction to a primary amine of a moiety suitable for the formation of a primary amino group; (b) has one epoxide moiety and is suitable for the formation of at least a primary amino group. It is characterized by the addition reaction of the branched molecule having at least one moiety to the primary amino moiety produced in (a) and (c) the addition reaction of the dendrimer to the amino functional group by at least a substituted or unsubstituted acrylate. It can be prepared by a continuous repetition of the stop reaction. The termination reaction can be carried out using (2,3-epoxypropoxy) (meth) acrylate. The epoxide amine dendrimer is described in US Pat. No. '142. The explanations of No. 5,760,142, column 1, line 65 to column 3, line 56 are incorporated herein by reference.

In other non-limiting embodiments, the dendrimer is a carbosilane-based polymer. Such dendrimers include a central silane core and (a) a carbosilane core having a plurality of carbosilane branches extending outward from the central core (each terminal branch has a silane terminal), and (b) around the core. Contains an additional polymer chain extending from the silane end. In one non-limiting embodiment, the number of additional polymer arms is at least 48. The description of the carbosilane dendrimer is incorporated herein by reference in US Pat. No. 5,276,110, specifically in column 1, line 58-column 5, line 5. ..

In another non-limiting embodiment, the dendrimer is prepared by polycondensation of diisopropanolamine and cyclic anhydride. These dendrimers are from DSM NV to HYBRANE^TMIt is sold under the name of, and is prepared by an acrylic acid ester and a methacrylic acid ester terminal group. Examples of HYBRANE dendrimers include commercially available H1500 (non-denatured) materials.

In a further non-limiting embodiment, the dendrimer is a polysiloxane polymer and can be prepared by repeated silane hydroxylation and chloride substitution at the silicon position. Specific methods of preparing these dendrimers are described in Uchida et al., J. AM. Chem. Soc., 1990, 112, 7077-7079, the entire description of which is incorporated herein by reference. .. See also U.S. Pat. No. 6,889,735 B2, column 5, lines 60-sixteen, line 13, which is incorporated herein by reference.

According to a non-limiting embodiment of the present invention, a composition comprising a dendritic polymeric acrylate is used to prepare a clear photochromic coating for a hard substrate. Such a photochromic coating and a method of preparing a composition containing the coating and applying it to a hard substrate will be described in particular in relation to the following description of the photochromic coating prepared of dendritic polyester acrylates. However, one of ordinary skill in the art can readily use any of the dendrimers described above (or subsequently developed dendrimers) instead of polyester dendrimers that have used acrylates to prepare such photochromic coatings. Is possible.

Non-acrylic dendritic polyester-type macromolecules are described, among others, in US Pat. Nos. 5,418,301, 5,663,247, 6,225,404 B1, and US Patent Application Publication No. 2002/0151652A1. These macromolecules are generally three-dimensional molecules with a dendritic structure. As used herein, the terms "dendritic polyester macromolecule" and "dendritic polyester oligomer" (or terms to the same effect) include hyperbranched dendritic macromolecules and dendrimers. Intended as. Dendrimers can be referred to as monodisperse or substantially monodisperse hyperbranched dendritic polymers.

Superbranched dendritic polyester macromolecules usually have an initiator or nucleus with one or more reaction sites or reaction functional groups, and many branched layers, and optionally one or more spacing layers and /. Alternatively, it contains a layer of chain-terminated molecules. Replication of continuous branched layers usually increases the multiplicity of branches and, if appropriate or desired, the number of terminal functional groups. This layer is commonly referred to as generational and branched dendrons. The hyperbranched dendrimer is described by the formula described in US Pat. No. 6,225,404 B1, column 6, lines 8-30, the description of which is incorporated herein by reference. can do. In these formulas, X and Y are initiators or nuclei with 4 and 2 reactive functional groups, respectively, and A, B and C are 3 (A and C) and 4 (B) reactions. It is a branched chain length initiator having a sex functional group, and each branched chain length extender forms one branched chain generation in a macromolecule. T in the above formula is a terminal chain stopper or a suitable terminal functional group or terminal moiety (eg, hydroxyl group, carboxyl group or epoxide group).

Dendron may be prepared in advance and then added to the nucleus. Dendron is monofunctional, bifunctional, for example, by condensation of one or more hydroxyfunctional carboxylic acids at normal esterification temperatures, or to monofunctional, bifunctional, trifunctional or polyfunctional carboxylic acids. It can be prepared by forming ester bonds with functional, trifunctional or polyfunctional alcohols or epoxides, or by similar procedures for forming ester bonds, ether bonds, and other chemical bonds. The raw materials used to produce dendron are selected to provide at least one terminal reaction site that reacts with the nucleus or initiator.

The dendritic polyester macromolecule is generally synthesized from an ester or polyester moiety (in combination with an ether or polyether moiety as needed). This hyperbranched dendritic macromolecule contains a monomer or polymer nucleus with at least one reactive epoxide group, hydroxyl group, carboxyl group, or anhydride group, with 1 to 100 nuclei. Generally 1 to 20, for example 2 to 8 branching generations, and at least one spacing generation with at least one chain length extender, if desired, are added, and the number of branching generations is at least three. It contains at least one monomer or polymer branched chain length extender containing a reactive group, one of which is a hydroxyl group and at least one of which is a carboxyl or anhydride group. This spacing chain extender is a compound having two reactive groups (one is a hydroxyl group and one is a carboxyl or anhydride group), or the internal ether of such a compound. (For example, a lactone component). The terminal chain length extender functional group of the superbranched dendritic macromolecule is substantially a hydroxyl group, a carboxyl group or an anhydride group, and the superbranched dendritic macromolecule may be optionally Completely or partially chain-stopped and / or functionalized by at least one monomer or polymer chain stopper.

A dendritic polyester-type macromolecule is a well-defined hyperbranched macromolecule that extends radially from the core and, as discussed, is synthesized by a series of stepwise and repetitive bifurcation reactions. This series of repeated branching reactions generally guarantees a complete shell for each generation, so that macromolecules are generally monodisperse. The synthetic procedure for the preparation of this dendritic polyester macromolecule provides nearly complete control over its size, shape, interface / inner surface chemistry, flexibility and topology. This dendritic polyester macromolecule can have perfect and symmetric bifurcations and incomplete and asymmetric bifurcations.

Non-limiting examples of central starting molecules for polyester dendritic macromolecules include aliphatic, alicyclic or aromatic diols, triol, tetraol, sorbitol, mannitol, dipentaerythritol, divalent, trivalent, Alternatively, a reaction product of a polyhydric alcohol and an alkylene oxide (eg, ethylene oxide, propylene oxide and butylene oxide) having a molecular weight of less than 2000 is included. Non-limiting examples of suitable diols include 1,3-propanediol, 1,3-propanediol dimer, trimmer or polymer, 2-alkyl-1,3-propanediol, 2,2-dialkyl-1. , 3-Propanediol (eg 2-butyl-2-ethyl-1,3-propanediol), 2-hydroxy-2-alkyl-1,3-propanediol, 2,2-di (hydroxyalkyl) -1 , 3-Propanediol, 2-hydroxyalkoxy-2-alkyl-1,3-propanediol, 2,2-di (hydroxyalkoxy) -1,3-propanediol, 1,2-propanediol, 1,3- Butanediol, 1,2-ethanediol, 1,4-butanediol, 1,5-pentanediol, neopentylglycol, trimethylolethane, trimethylolpropane, pentaerythritol, ditrimethylolethane, ditrimethylolpropane, 1,6 -Hexanediol and poly tetrahydrofuran are included. The alkyl group of this initiator molecule is generally C₁~ C₁₂Alkyl group (eg C₁~ C₄Alkyl group).

Polyester chain length extenders are monofunctional carboxylic acids having at least two hydroxyl groups, such as dimethylol propionic acid, α, α-bis (hydroxy) propionic acid, α, α-bis (hydroxymethyl) propion. Acid, α, α-bis (hydroxymethyl) butyric acid, α, α-bis (hydroxymethyl) tartaric acid, α, α, α-tris (hydroxymethyl) acetic acid, α, α-bis (hydroxymethyl) butyric acid, α , β-Dihydroxypropionic acid, heptonic acid, citric acid, d-tartaric acid or l-tartaric acid, or α-phenylcarboxylic acid (eg, 3,5-dihydroxybenzoic acid), but not limited to these.

Chain terminators that can be used include saturated monofunctional carboxylic acids, saturated fatty acids, unsaturated monofunctional carboxylic acids, aromatic monofunctional carboxylic acids (eg, benzoic acid), and bifunctional or polyfunctional. Includes, but is not limited to, carboxylic acids, or anhydrides thereof. Non-limiting examples of such acids include behenic acid. The terminal hydroxyl groups of the polyester chain extender can react with the chain stopper with or without functional groups.

The dendritic polyester macromolecules are commercially available from Perstorp Specialty Chemicals (Swedish Pestorp) under the names BOLTORN® H20 dendritic polymer, BOLTORN® H30 dendritic polymer and BOLTORN® H40 dendritic polymer. These macromolecules are functionalized with hydroxy groups at the ends. These materials generally have an average molecular weight in the range of 1,000-4000. The BOLTORN® H20, BOLTORN® H30, and BOLTORN® H40 each have an average of 16, 32, and 64 hydroxy groups at the ends of the macromolecule.

The dendritic polyester macromolecular material is acrylicized by known esterification techniques to form the optically quality dendritic polyester acrylate resin used to prepare the photochromic coatings described herein. Can provide the materials used for. See, for example, International Publication Nos. 00/77070A2 and 00/64975.

Acrylicization of dendritic polyester macromolecules and recovery and purification of acrylicized dendritic polyester macromolecules are described, for example, in Kirk-Othmer Encyclopedia of Chemical Technology (1980, Volume 1, It can be performed using methods well known in the literature, such as those described in the article "Acrylic Ester Polymers" in pp.386-413). Acrylicization is generally a direct reaction (eg, esterification) of a molecule to be acrylicized with, for example, acrylic acid, methacrylic acid, or crotonic acid (β-methacrylic acid), condensation with isocyanato (meth) acrylate, Alternatively, it is a direct reaction with the anhydride and / or halide corresponding to the acrylic acid, and the molar ratio of the hydroxyl group to the acid, the anhydride and / or the halide is generally 1: 0.1 to 1: 1. Between 5, and more generally between 1: 0.5 and 1: 1.5. Other non-limiting examples of acrylate agents include epoxides, or anhydrous functional acrylates and methacrylates (eg, glycidyl methacrylate). In non-limiting embodiments, the acrylate agent is used in stoichiometrically excessive molar amounts.

The proportion of functional acrylic acid groups (eg, acrylicized hydroxyl groups) in the acrylicized dendritic polyester macromolecules may vary and is generally 5-100% of the initial hydroxyl group content. The range. In an alternative non-limiting embodiment, the proportion of functional acrylic acid groups in the acrylicized dendritic polyester macromolecule is in the range of 20-90%, eg 40-85% (eg 45-80%). It may change. The ratio of acrylicized hydroxyl groups may be in the range of any combination of these ratios (including the listed ratios).

The esterification procedure is generally carried out in the presence of a solvent such as a non-polar organic solvent solution. Non-limiting examples of such solvents include, but are not limited to, heptane, cyclohexane, toluene, benzene, xylene, or mixtures of such solvents. The esterification procedure conveniently comprises, for example, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, sulfuric acid, phosphoric acid, naphthalenesulfonic acid, Lewis acid (eg, BF).₃, AlCl₃, SnCl₄), Titanate (eg, tetrabutyl titanate), organotin compounds, etc., but not limited to these. Generally, the acrylicization procedure is carried out at a temperature in the range of 50-200 ° C, for example in the range of 80-150 ° C. The temperature of acrylicization may vary and generally depends on the solvent selected and the pressure at which the acrylicization procedure is performed. This acrylicization procedure is performed in the presence of radical polymerization initiators (eg, but not limited to methyl ether hydroquinone, hydroquinone, phenothiazine, di-t-butylhydroquinone) and mixtures of such initiators. obtain.

According to the disclosure of International Patent Publication No. 00/64975, dendritic polymer macromolecules (eg, dendritic polyester macromolecules) are generally highly viscous liquids, so one or more hydroxyl groups should be added before the acrylicization procedure. It can be mixed with organic alcohols (eg, fatty alcohols) that have and have a molecular weight of less than 2000 (eg, in the range of 60-1500, or 100-1000). Generally, the alcohol is liquid at temperatures in the range of 20 ° C to 50 ° C, or at this temperature a liquid mixture with dendritic macromolecular macromolecules is obtained. The alcohol can be a diol. Non-limiting embodiments of diols include ethylene glycol, 1,2-propylene glycol or 1,3-propylene glycol, butanediol, or diglycol, triglycol or polyglycol, and examples thereof include diethylene glycol. , Polypropylene glycol, or glycol polymers such as polymers containing one or more ethylene glycols and one or more propylene glycols. The weight ratio of the dendritic polymer macromolecule to the alcohol may vary. In general, the weight ratio of dendritic macromolecular macromolecules to alcohol may vary from 90:10 to 10:90. In alternative non-limiting embodiments, the weight ratio of dendritic macromolecular macromolecules to alcohol can vary between 25:75 and 75:25, or between 40:60 and 60:40, eg, 50: It is 50. The weight ratio of dendritic polyester macromolecules to alcohols may vary between the listed values (including those listed values). Acrylicization of this mixture produces an acrylate compound containing at least one dendritic polymeric acrylate and at least one acrylate monomer.

In a non-limiting embodiment, the radiation curable acrylic monomer material may be included in a composition comprising a dendritic polyester acrylate. Non-limiting examples of radiation curable acrylic monomer materials include monoacrylates and polyacrylates (eg diacrylates, triacrylates, tetraacrylates, pentaacrylates). For example, monoacrylates such as monomers containing a single acrylic functional group include, but are not limited to, hydroxy-substituted monoacrylates and alkoxysilylalkyl acrylates (eg, trialkoxysilylpropylmethacrylate). In one non-limiting embodiment, the radiation curable monomer material is selected from diacrylates, triacrylates, and mixtures of such polyacrylates.

The weight ratio of the radiation curable acrylic monomer material to the dendritic polymer acrylate in the composition containing the dendritic polymer acrylate may vary and is generally the physical properties of the curable mixture (eg, viscosity of the mixture, degree of cross-linking). , And the hardness of the coating). In a non-limiting embodiment, the weight ratio of the dendritic polymeric acrylate to the radiation curable acrylic monomer material can be in the range 90:10 to 10:90. In alternative non-limiting embodiments, this weight ratio can range from 70:30 to 30:70 (eg, 40:60 to 60:40, eg 50:50). The weight ratio of the dendritic polyester acrylate to the radiation curable acrylic monomer material may vary between the listed values (including the listed values).

The weight ratio of the dendritic polymeric acrylate to the commonly selected radiation curable acrylic monomer material is selected to provide the desired balance between the physical characteristics of the coating and the photochromic performance of the coating. In general, softer coatings enhance photochromic kinetic performance (eg, activation (degree of activation and time to activation) and photochromic deactivation (time to fading)). The hardness (softness) of the coating can be measured by techniques well known to those skilled in the art (eg, Fischer microhardness, pencil hardness, or Knoop hardness). Fischer microhardness values are 100 millinewtons deep with a 2 μm (micron) indentor (Vickers diamond needle) using a Fischerscope HCV Model-H-100 device (sold by Fischer Technology, Inc.). It can be obtained by measuring 3 times in the central region of the test sample under the condition of loading, 30 loading procedures, and a 0.5 second rest between loading procedures.

The acrylic monomer material can be represented by the following general chemical formula (I): R -[OC (O) C (R') = CH₂]_n I In the formula, R "is an aliphatic or aromatic group containing 2 to 20 carbon atoms and optionally 1 to 20 alkyleneoxy bonds; R'is hydrogen or 1 to 4 carbons. It is an atomic-containing alkyl group, where n is an integer from 1 to 5. If n is greater than 1, R "is a linking group that bonds together the acrylic functional groups. In general, R'is hydrogen or methyl and n is an integer in the range 1-3. The diacrylate (when n is 2) can be represented by the following general formula (II):

<chemistry num="1"><img id="000002" he="29" wi="120" file="JP5259407B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>In the formula, R₁And R₂Can be the same or different, each selected from hydrogen or an alkyl group containing 1 to 4 carbon atoms (eg, methyl), where A is a hydrocarbyl linkage of, for example, 1 to 20 carbon atoms. Groups, eg, alkylene groups, one or more oxyalkylene groups [or mixtures of different oxyalkylene groups]; or the following General Chemical Formula (III):

<chemistry num="2"><img id="000003" he="31" wi="131" file="JP5259407B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>In the formula, each R₃Is an alkyl group of hydrogen, hydroxy or 1 to 4 carbon atoms (eg, methyl); X is a halogen atom (eg, chlorine); a is an integer of 0 to 4 (eg, 0 to 1). Represents the number of halogen atoms substituted on the benzene ring; k and m are numbers in the range 0-20 (eg, 1-15 or 2-10). The values of k and m are average numbers and may be integers or fractions when calculated.

An acrylate having an epoxy group can be represented by the following general chemical formula (IV):

<chemistry num="3"><img id="000004" he="29" wi="114" file="JP5259407B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>In the formula, R₁And R₆May be the same or different, each selected from hydrogen or an alkyl group containing 1 to 4 carbon atoms (eg, methyl); R₄And R₅Is an alkylene group containing 2-3 carbon atoms (eg ethyleneoxy and propyleneoxy), where m and n are numbers in the range 0-20, eg 0 or 1-15, or 2-10. .. If one of m and n is 0 and the other is 1, the remaining R groups are aromatic groups of the following general chemical formula (V):

<chemistry num="4"><img id="000005" he="31" wi="76" file="JP5259407B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>For example, it can be a group derived from the 2,2'-diphenylene propane group, which phenyl group is C.₁~ C₄It can be replaced with an alkyl group or halogen (eg, methyl and / or chlorine).

In the non-limiting examples of acrylic monomer materials listed below, the term "acrylate" as defined above includes the corresponding lower alkyl substituted acrylate (eg, the corresponding methacrylate) and vice versa. For example, references to hydroxyethyl acrylates include hydroxyethyl methacrylate, hydroxyethyl etacrylate and the like; references to ethylene glycol diacrylates include, for example, ethylene glycol dimethacrylate, ethylene glycol dietacrylate and the like. Non-limiting examples of acrylic monomer materials include: Hydroxyethyl acrylate, Hydroxypropyl acrylate, Hydroxybutyl acrylate, Hydroxy-poly (alkyleneoxy) alkyl acrylate, Caprolactone acrylate, Ethylene glycol diacrylate, Butanediol diacrylate, Hexanediol diacrylate, Hexamethylenediacrylate, Diethylene glycol diacrylate, Triethylene glycol diacrylate, Tetraethylene glycol diacrylate, Polyethylene glycol diacrylate, Dipropylene glycol diacrylate, Tripropylene glycol diacrylate, Tetra Propylene Glycol Diacrylate, Polypropylene glycol diacrylate, Glyceryl ethoxylate diacrylate, Glyceryl propoxylate diacrylate, Trimethylolpropane triacrylate Trimethylolpropane ethoxylate triacrylate, Trimethylolpropane propoxylate triacrylate, Neopentyl glycol diacrylate, Neopentyl glycol ethoxylate diacrylate, Neopentyl glycol propoxylate diacrylate, Monomethoxytrimethylolpropane ethoxylate diacrylate, Pentaerythritol ethoxylate tetraacrylate, Pentaerythritol propoxylate tetraacrylate, Dipentaerythritol pentaacrylate, Dipentaerythritol ethoxylate pentaacrylate, Dipentaerythritol propoxylate pentaacrylate, Di-trimethylolpropane ethoxylate tetraacrylate, Bisphenol A ethoxylate diacrylate with 2 to 30 ethoxy groups, Bisphenol A propoxylate diacrylate with 2-30 propoxy groups, Bisphenol A alkoxylated diacrylate, containing a mixture of 2-30 ethoxy and propoxy groups, Bisphenol A glycerolate dimethacrylate, Bisphenol A glycerolate (1glycerol / 1phenol) dimethacrylate, Glycidyl acrylate, β-Methylglycidyl acrylate, Bisphenol A-monoglycidyl ether acrylate, 4-Glysidyloxybutyl methacrylate, 3- (Glysidyl-2-oxyethoxy) -2-hydroxypropyl methacrylate, 3- (Glysidyloxy-1-isopropyloxy) -2-hydroxypropyl acrylate, 3- (Glysidyloxy-2-hydroxypropyloxy) -2-hydroxypropyl acrylate, and 3- (Trimethoxysilyl) propyl methacrylate.

Many radiation curable acrylic materials are commercially available; if not, they can be prepared by procedures well known to those of skill in the art. For non-limiting examples of commercially available acrylate materials, the disclosure of which is incorporated herein by reference in particular, US Pat. No. 5,910,375, column 8, lines 20-55 and column 10, paragraph 5. It is described on the 36th line. Acrylic materials on the market are sold by various manufacturers, including those sold under the trade names SARTOMER, EBECRYL and PHOTOMER.

In a further non-limiting embodiment, the reactive bifunctional acrylic monomer material represented by the following general chemical formula (VI) may be included in a composition comprising a dendritic polymeric acrylate:

<chemistry num="5"><img id="000006" he="34" wi="131" file="JP5259407B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>In the formula, each R₁Is hydrogen or methyl, x, y and z are positive numbers respectively, and the sum of x, y and z is in the range 9-30. For a more detailed description of the monomer represented by General Chemical Formula (VI), the disclosure is incorporated herein by reference in US Pat. No. 6,602,603, column 5, lines 1-25, and It is described in the same issue, column 6, lines 28-37.

In yet another non-limiting embodiment of the invention, a composition comprising a dendritic polymeric acrylate comprises (1) at least one material (eg, a carbonate group) comprising at least one carbonate group and at least one hydroxyl group. Alcohol or polyol containing), or an acrylic monomer containing at least one carbonate group and at least one hydroxyl group (eg, a polycarbonate polyol), and (2) a material containing at least one monoisocyanate group and at least one unsaturated group (containing). For example, it may contain a reaction product of an acrylic monomer (reaction product) containing a vinyl ether group and an isocyanate group. For a detailed explanation of such reaction products, the disclosure contents are incorporated herein by reference, and International Patent Publication No. 03/037998A1, p. 8 (p. 32) to p. 15 (p. 16), and p. It is described on page 15, line 37 to page 22, line 19.

In a further non-limiting embodiment, reactive monomers / diluents (eg, monomers containing radiocurable or thermosetting ethylene or allyl functional groups (excluding acrylic functional groups)) are also dendritic polymers. It may be present in compositions containing acrylates. Non-limiting examples of such materials include, but are not limited to, radiation curable vinyl compounds (eg, vinyl ethers). Generally, the reactive monomer / diluent can be present in the composition in an amount of up to 20% by weight (eg, in the range of 0-10% by weight) (relative to the resin solid). The amount of this reactive monomer / diluent may vary arbitrarily between specific amounts, including the listed values. The particular amount used will vary depending on the final physical properties desired for the curable composition and the coating obtained from it, as described in connection with the radiation curable acrylic monomer material.

Compounds with vinyl ether groups that can be used in radiation curable compositions containing dendritic polyester acrylates include alkyl vinyl ethers with terminal groups substituted with hydrogen atoms, halogen atoms, hydroxyl groups, and amino groups; hydrogen atoms, halogens. Cycloalkyl vinyl ethers with terminal groups substituted with atoms, hydroxyl groups, and amino groups; monovinyl ethers, divinyl ethers and polyvinyl ethers with vinyl ether groups bonded to alkylene groups, and vinyl ether groups with alkyl groups, cycloalkyl groups, and aromatics. Monovinyl ethers, divinyl ethers and polyvinyl ethers bonded to at least one group with or without a substituent selected from the group groups via at least one bond selected from ether bonds, urethane bonds and ester bonds. Included, but not limited to. See, for example, the vinyl ethers described in US Pat. No. 6,410,611 B1, column 19, lines 26-20, line 27, the disclosure of which is incorporated herein by reference.

The amount of the acrylic monomer and the reactive monomer / diluent described above is an amount with respect to the total amount of the polymerizable material (resin solid) in the composition containing the dendritic polymer acrylate, and is an amount of the non-polymerizable organic diluent (for example,). It does not contain other non-polymerizable components such as solvents, photoinitiators, stabilizers, plasticizers and other such components). The sum of all the various components, including the photochromic coating composition, is of course equal to 100%.

Compositions comprising dendritic polymeric acrylates may contain additives (adulides) that enhance the effectiveness of the resulting photochromic coating. Such additives include adhesion-promoting additives, UV stabilizers, hindered amine stabilizers, mold release agents, viscous additives, fluidity additives, smoothing agents, wetting agents, defoaming agents, rheology modifiers, surfactants. Includes, but is not limited to, activators (eg, fluorosurfactants), antioxidants. Such materials are well known to those of skill in the art. For non-limiting examples of commercially available surfactants, antioxidants, and stabilizers, US Pat. No. 5,910,375, column 10, lines 43-54, the disclosure of which is incorporated herein by reference. It is mentioned in the eyes. Other non-limiting examples of such additives include silicones, modified silicones, silicone acrylates, hydrocarbons and fluorine-containing compounds.

According to non-limiting embodiments, it is contemplated that an amount of at least one adhesion promoting material (fixing agent) that enhances adhesion may be incorporated into a curable composition comprising a dendritic polymeric acrylate. .. The amount of enhanced adhesion is the conformity of the photochromic-containing dendritic polymer acrylate coating to the superimposed organosilane-containing abrasion resistant coating (described herein) applied to the dendritic polymer acrylate coating. It means that the sex is strengthened. In general, at least one fixer may be incorporated into the composition in an amount of 0.1-20% by weight (relative to the resin solid) prior to applying the composition containing the dendritic polymeric acrylate to the substrate. In an alternative non-limiting embodiment, at least one fixer 0.5-16 (eg, 0.5-10)% by weight, or 0.5-8 (eg, 5)% by weight is incorporated into the dendritic polymeric acrylate composition. You may. The amount of fixer incorporated into the dendritic polyester acrylate composition can range (including the listed values) between any combination of the above values.

Adhesion of aminoorganosilane, etc. to the fixer that may be incorporated into the dendritic polymeric acrylate coating to enhance compatibility with wear resistant coatings (eg, abrasion resistant coatings containing organosilane materials) Includes, but is not limited to, accelerated organosilane materials, as well as silane coupling agents, organic titanic acid coupling agents, and organic lead zirconate coupling agents.

A photochromic coating composition comprising a dendritic polymeric acrylate may also include a UV stabilizer, which may be a UV absorber and / or a hindered amine light stabilizer (HALS). Non-limiting examples of UV absorbers include benzotriazoles and hydroxybenzophenones. When using UV absorbers, it should be noted that sufficient UV radiation of the appropriate wavelength can pass through the coating and activate the photochromic material within the photochromic coating. HALS stabilizers are marketed by Ciba-Geigy under the name TINUVIN. The amount of light stabilizer used is an effective amount (eg, an effective amount) to stabilize the composition, which will vary depending on the particular compound selected. In non-limiting embodiments, the amount of light stabilizer used is generally up to 20 parts by weight relative to 100 parts by weight of the monomer / polymer component of the dendritic polymeric acrylate composition. UV absorbers are also used in effective amounts, and in non-limiting embodiments, generally up to 10 parts by weight (eg 0.05-5 parts by weight) per 100 parts by weight of the dendritic polymeric acrylate composition. is there.

Also, in order to dissolve and / or disperse the components containing the coating composition containing the dendritic polymer acrylate, a solvent may also be present in the coating composition. Generally, a solvating amount of solvent (eg, an amount sufficient to solubilize / disperse the solid component in the coating composition) is used. In non-limiting embodiments, 10-80% by weight of solvent material is used relative to the total weight of the coating composition.

Non-limiting solvents include benzene, toluene, methyl ethyl ketone, methyl isobutyl ketone, acetone, ethanol, tetrahydrofurfuryl alcohol, propyl alcohol, propylene carbonate, N-methylpyrrolidinone, N-vinylpyrrolidinone, N-acetylpyrrolidinone, N- Hydroxymethylpyrrolidinone, N-butylpyrrolidinone, N-ethylpyrrolidinone, N- (N-octyl) pyrrolidinone, N- (N-dodecyl) pyrrolidinone, 2-methoxyethyl ether, xylene, cyclohexane, 3-methylcyclohexane, ethyl acetate, Butyl acetate, tetrahydrofuran, methanol, amyl propionate, methyl propionate, propylene glycol methyl ether, diethylene glycol monobutyl ether, dimethyl sulfoxide, dimethylformamide, ethylene glycol, ethylene glycol monoalkyl ethers and dialkyl ethers and their derivatives (these are: Includes CELLOSOLVE industrial solvents and (sold as mixtures of such solvents).

The dendritic polymeric acrylate (eg, dendritic polyester acrylate) and compositions containing such acrylates can be cured with or without the use of photoinitiators. Although these materials can cure without a photoinitiator, the use of a small amount of one or more photoinitiators can increase the rate of cure and result in a more perfect cure in a shorter amount of time. Of course, no photoinitiator is required when the dendritic polymeric acrylic resin formulation is cured by electron beam irradiation.

When a photoinitiator is used, the photoinitiator is present in an amount sufficient to initiate and sustain curing of the composition (eg, initiating amount or photoinitiating amount). The photoinitiator is preferably used in the minimum amount required to initiate the curing process. In an alternative non-limiting embodiment, the photoinitiator is 0.1-10% by weight, for example 0.5-6, based on the total weight of the radiation curable polymerizable component in the curable composition comprising the dendritic polymeric acrylate. It is present in an amount of% by weight, more generally 0.5 to 1% by weight.

Photoinitiators are well known to those of skill in the art. Photoinitiators, which are free radical initiators, fall into two major groups based on their mode of action. Cleavage photoinitiators include, but are not limited to, acetphenone, α-aminoalkylphenone, benzoin ethers, benzoyloximes, acylphosphine oxides, and bisacylphosphine oxides. Withdrawal photoinitiators include, but are not limited to, benzophenone, Michler ketone, thioxanthone, anthraquinone, camphorquinone, fluorone, and ketocoumarin. Plot-type photoinitiators work better in the presence of amines and other substances such as hydrogen-donating materials that are added to provide unstable hydrogen atoms for abstraction. Typical hydrogen donors have active hydrogen at the α position with respect to oxygen or nitrogen (eg, alcohols, ethers and tertiary amines) or have active hydrogen atoms directly attached to sulfur (eg, thiols). .. Even in the absence of such additive materials, photoinitiation can still occur due to the extraction of hydrogen from the monomers, oligomers, or other components of the system.

Non-limiting examples of photopolymerization initiators that can be used include benzyl, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzophenol, acetophenone, benzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis ( N, N'-dimethylamino) benzophenone, diethoxyacetophenone, fluorone (eg Spectra Group) H-Nu series of initiators sold by Limited), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-isopropylthioxanthone, α-aminoalkylphenone (eg , 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, acylphosphine oxide (eg, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide) , 2,6-dichlorobenzoyldiphenylphosphine oxide, and 2,6-dimethoxybenzoyldiphenylphosphine oxide); bisacylphosphine oxide (eg, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide) , Bis (2,6-dimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide, and bis (2, 6-Dichlorobenzoyl) -2,4,4-trimethylpentylphosphine oxide); phenyl-4-octyloxyphenyliodonium hexafluoroantimonate, dodecyldiphenyliodonium hexafluoroantimonate, (4- (2-tetradecanol) oxy) Includes phenyl) -iodonium hexafluoroantimonates and mixtures of photoinitiators thereof. For examples of commercially available photoinitiators, the disclosure of which is incorporated herein by reference, US Pat. No. 5,910,375. No. 10, columns 38-43, and US Pat. No. 6,271,339 B1, column 11, lines 24-65.

Curable compositions that include a dendritic polyester acrylate in addition to the photoinitiator can cure other reactive monomers in the thermal initiator (eg, peroxy or azo type initiator) or coating composition. A catalyst to help may also be included. The choice (and amount) of such further initiator / catalyst will vary depending on the conditions required to initiate the reaction of the reactive monomer / diluent used, and the conditions required to initiate such reaction will be those of skill in the art. Is well known.

Curable photochromic coating compositions containing dendritic polymeric acrylates are prepared by mixing the components of the composition at a temperature that facilitates mixing and blending. The composition is then applied to a hard substrate by techniques recognized and well known to those skilled in the art (eg, spin coating, dip coating, curtain coating, spray coating) or by the methods used in the preparation of topcoats. be able to. Such a method is described in US Pat. No. 4,873,029.

Before applying the photochromic coating to the surface of the substrate, the surface of the substrate is often cleaned and treated to provide a clean surface and a surface that enhances the adhesion of the photochromic coating to the substrate. .. Effective cleaning and treatment commonly used include, but are not limited to, ultrasonic cleaning with aqueous soap / detergent solution, aqueous mixture of organic solvents (eg, isopropanol: water or ethanol: 50:50 mixture of water). Cleaning with water, UV treatment, active gas treatment (eg, treatment with low temperature plasma or corona discharge), and chemical treatment that causes hydroxylation of the substrate surface (eg, alkali metal hydroxide such as sodium hydroxide or potassium hydroxide). Surface etching with aqueous solution) is included, and this solution may contain fluorosurfactants. Generally, the alkali metal hydroxide solution is a diluted aqueous solution (eg, 5-40% by weight of alkali metal hydroxide, more typically 10 to 15% by weight, for example 12% by weight). For example, U.S. Pat. Nos. 3,971,872, column 3, lines 13-25, column 4,904,525, column 6, lines 10-48, and column 5,104,692, column 13, which describe the surface treatment of polymer organic materials. See lines 10-59. Such disclosures are incorporated herein by reference.

In non-limiting embodiments, it is possible to use low temperature plasma treatment for the surface treatment of the substrate. This method enhances the adhesion of the superposed film or coating by surface treatment and, for example, by roughening and / or chemically modifying the surface without affecting the rest of the article. It is a clean and effective way to change the physical surface. An inert gas (eg, argon, etc.) and a reactive gas (eg, oxygen) are used as the plasma gas. Inert gases roughen the surface, while reactive gases such as oxygen roughen the surface exposed to plasma (eg, by creating hydroxyl sites or carboxyl units on the surface) and are slightly chemically. Denature. The degree of surface roughness and / or chemical denaturation depends on the operating conditions of the plasma gas and the plasma apparatus (including the length of processing time).

In non-limiting embodiments, it is also possible to apply the primer to the surface of the substrate prior to applying the photochromic coating. The primer is inserted between the substrate and the photochromic coating as a barrier coating to prevent the interaction of the ingredients containing the photochromic coating with the substrate (and vice versa) and / or the base of the coating. It serves as an adhesive layer that enhances the adhesiveness to the material. The undercoat can be applied to the substrate by any of the conventional methods known to those skilled in the art of applying the coating (eg, spray coating, spin coating, spread coating, curtain coating, roll coating or dip coating). It can be applied to a cleaned untreated surface of a substrate or a cleaned treated surface (eg, a chemically treated surface). Undercoats are well known to those of skill in the art. The choice of proper undercoat depends on the substrate used and the particular photochromic coating.

The undercoat thickness can be one or more monolayers. In non-limiting embodiments, the undercoat thickness can range from 0.1 to 10 microns. In alternative non-limiting embodiments, the undercoat thickness can range from 0.1 to 2 or 3 microns. The undercoat thickness may vary between any combination of the above values (including the listed values). In an alternative non-limiting embodiment, the undercoat is a composition comprising an organic functional silane as described in US Pat. No. 6,150,430, or substantially organic as described in US Pat. No. 6,025,026. It is a composition that does not contain siloxane.

Photochromic coating compositions containing dendritic polymeric acrylates (eg, dendritic polyester acrylates) are exposed to UV radiation (eg, radiation in the range of 200-450 nanometers) (or UV radiation is not used). If so, it may be cured (by electron beam processing). In one non-limiting embodiment, exposure to UV is a commercially available UV lamp or excimer lamp on a conveyor that moves the coating (eg, the substrate on which the coating is applied) at a predetermined rate. It can be done by passing underneath. This radiation may include both visible and ultraviolet spectra. This radiation may be monochromatic or pleochroic, non-coherent or coherent, and polymerized by the polymerizable component of the photochromic composition containing the dendritic polymeric acrylate. It should be strong enough to get started. The curing process is generally more effective with oxygen (eg, air) removed from the curing process. Oxygen elimination can be achieved by using a nitrogen blanket on the applied film during the curing process.

The cured radiation source used for photopolymerization is selected from ultraviolet and / or visible light sources. The radiation source is a mercury lamp, FeI₃And / or GaI₃It can be a mercury lamp, a germicidal lamp, a xenon lamp, a tungsten lamp, a metal halide lamp, or a combination of these lamps doped with. In general, the absorption spectrum of the photoinitiator is adapted to the spectral output of the light source bulb (eg, H sphere, D sphere, Q sphere and / or V sphere) for the highest curing efficiency. The exposure time of the curable coating to the light source depends on the wavelength and intensity of the light source, the photoinitiator, and the thickness of the coating. In general, the exposure time is sufficient to substantially cure the coating, or to prepare a coating that is sufficiently cured to allow subsequent physical treatment for thermal curing. It will be enough time. The time required for UV radiation curing or electron beam radiation curing is generally shorter than thermosetting (eg, 5 seconds to 5 minutes) and varies with radiation intensity (output).

The specific curing conditions used may vary. In general, the curing conditions depend on the particular substrate selected, the polymerizable component in the photochromic coating formulation, and the type of catalyst / initiator used, or, in the case of electron beam emission, the intensity of the electron beam. Change. Those skilled in the art of photopolymerization can easily determine the appropriate curing conditions to be used.

Although less desirable, the photochromic coating composition containing the dendritic polyester acrylate may be heat cured. For example, an azo-type or peroxy-type free radical heat initiator may be incorporated into the coating composition and the coating may be cured by infrared heating, for the coating (eg, a substrate containing the coating) to cure the coating. It may be cured by placing it in a conventional oven maintained at a sufficient temperature (eg, a convection oven). The heat initiator is preferably one that does not discolor the obtained coating or one that does not decompose the photochromic material incorporated in the polymerizable coating composition. The thermosetting process may include heating the photochromic coating from room temperature to a temperature below the temperature at which the substrate and photochromic material are damaged by the heating. For example, a typical thermosetting cycle can include heating the coating formulation from room temperature (22 ° C) to a temperature in the range of 85 ° C to 125 ° C for 2 to 20 minutes.

Non-limiting examples of suitable organic peroxy compounds include peroxymonocarbonate esters (eg, tertiary butylperoxyisopropyl carbonate); peroxydicarbonate esters (eg, di (2-ethylhexyl) peroxydicarbonate, di (first). Dibutyl) peroxydicarbonate, and diisopropylperoxydicarbonate); diacyl peroxides (eg, 2,4-dichlorobenzoyl peroxide, isobutyryl peroxide, decanoyl peroxide, lauroyl peroxide, propionyl peroxide, acetyl peroxide, benzoyl peroxide, p- Chlorobenzoyl peroxide); peroxyesters (eg, t-butylperoxypivalate, t-butylperoxyoctylate, and t-butylperoxyisobutyrate); methylethylketone peroxides; and acetylcyclohexanesulfonyl peroxides.

Non-limiting examples of suitable azobis (organic nitrile) compounds include azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylpentanenitrile), 1,1'-azobiscyclohexanecarbo. Includes nitriles, and azobis (2,4-dimethylvaleronitrile), as well as mixtures of such azo heat initiators.

If a coating that is physically treatable but not completely cured is produced under thermosetting or UV / electron beam curing conditions, a heat treatment may be performed after curing to completely cure the photochromic coating. .. Post-curing heat treatment procedures for complete curing of the film are usually suitable for heating in an oven at 212 ° F (100 ° C) for 0.5-3 hours. In a further exemplary embodiment, the photochromic dendritic polymeric acrylate coating may be cured with a combination of heat initiator and photoinitiator.

The hard substrate to which the photochromic dendritic polymer acrylate coating is applied may be changed. Such substrates have at least one surface that is suitable for photochromic coatings. Non-limiting examples of such hard substrates include paper, glass, ceramics, wood, stone, textiles, metals, and organic polymer materials. The particular substrate selected will vary depending on the particular application, which requires both a rigid substrate and a photochromic coating. In a non-limiting embodiment, the substrate is an optical substrate, such as a transparent substrate such as a lens. Non-limiting examples of lenses such as ocular lenses include planar lenses, semi-finished lenses, finished lenses, single-view lenses, semi-finished single-view lenses, progressive multifocal lenses, and finished single-view lenses. included.

Polymeric substrates that can be used in the preparation of the photochromic articles of the present invention include organic polymeric materials and glass. The term "glass" as used herein is defined as a polymeric substance (eg, a polymeric silicate). The glass substrate may be of any type as long as it is suitable for the intended purpose, but preferably transparent, light-colored transparent glass (well-known quartz glass), particularly soda limestone quartz glass. The properties and compositions of various quartz glasses are well known in the art. The glass substrate can be reinforced by either heat tempering or chemical tempering. Polymer organic substrates that can be used to prepare articles with photochromic coatings containing dendritic polymeric acrylates are such that they have a surface that is chemically compatible with and adapted to the photochromic dendritic polymeric acrylate coating. Any plastic material currently known (or later discovered). A non-limiting example of a polymeric organic substrate is an optically transparent note for optical applications such as synthetic resins recognized in the art as useful as optical substrates, such as ophthalmic lenses. Includes organic optical resins and the like used to prepare molds.

For organic substrates that can be used as polymeric organic substrates in non-limiting embodiments, the disclosure is incorporated herein by reference in US Pat. No. 5,658,501, column 15, line 28. ~ There are polymers (ie, homopolymers and copolymers) prepared from the monomers and mixtures of monomers disclosed in column 16, line 17. Such an organic substrate may be a thermoplastic or thermosetting polymeric substrate, such as a transparent substrate generally having a refractive index in the range of 1.48 to 1.74.

Non-limiting examples of such monomers and polymers include allyl diglycol carbonate, such as diethylene glycol bis, which is a polyol (allyl carbonate) monomer (eg, a monomer marketed by PPG Industries, Inc. under the CR-39 trademark. (Allyl carbonate)); Polyurea-polyurethane (polyurea urethane) polymer (for example, prepared by the reaction of a polyurethane prepolymer with a diamine hardener) (the disclosure of which is incorporated herein by reference, a US patent. No. 6,127,505, 1st column, 59th line to 6th column, 5th line), PPG Industries, Composition of one such polyurea urethane polymer marketed by Inc. under the TRIVEX trademark; acrylic functional monomers (eg, polyol (meth) acryloyl-terminated carbonate monomers, diethylene glycol dimethacrylate monomers, ethoxylated phenol methacrylate monomers, ethoxy Trimethylol propantriacrylate monomer, ethylene glycol bismethacrylate monomer, poly (ethylene glycol) bismethacrylate monomer, urethane acrylate monomer, and poly (ethoxylated bisphenol A dimethacrylate) monomer, but not limited to these); Benzene Monomer; Poly (Vinyl Acetate); Poly (Vinyl Alcohol); Poly (Vinyl Chloride); Poly (Vinylidene Chloride); Polyethylene; Polypropylene; Polyurethane; Polythiourethane (eg Mitsui Toatsu Chemicals, Materials such as, but not limited to, MR-6, MR-7, and MR-8 optical resins from Inc.; thermoplastic polycarbonates such as carbonate-bonded resins derived from bisphenol A and phosgen (such. One of the substances sold under the LEXAN trademark); Polyester (eg, a substance marketed under the MYLAR trademark); Poly (ethylene terephthalate); Polyvinyl butyral; Poly (methyl methacrylate) (eg, marketed under the PLEXIGLAS trademark) Substance), and polyisocyanates and polythiols or polyepisulfide monomers (either by homopolymerization or copolymerization with polythiol and / or terpolymerization), polyisocyanates, polyisothiocianates, and optionally ethylenic. Includes polymers, which are prepared by reaction with unsaturated monomers or halogenated aromatic-containing vinyl monomers. Copolymers of such monomers and blends of the listed polymers, as well as copolymers with other polymers, are also contemplated (eg, to form interpenetrating network products). In non-limiting embodiments, the organic polymeric substrate has chemical compatibility with the photochromic polymeric coating applied to the surface of the substrate, and for optical applications the substrate is preferably transparent.

The polymeric organic substrate used to prepare the photochromic articles of the present invention may have a protective coating (eg, an abrasion resistant coating) on its surface. For example, commercially available thermoplastic polycarbonate optical lenses are generally sold with a wear-resistant coating (eg, hard coat) pre-applied to the surface because the surface is easily scratched, worn, or worn. There is. An example of such a lens is the Gentex Polycarbonate Lens (Gentex). (Sold by Optics) is included, and this lens is sold with a hard coat pre-applied to the polycarbonate surface. As used in the present disclosure and claims, the term "polymer organic substrate" (or a term to the same effect) or the term "surface" of such a substrate means the polymer organic substrate itself or a group. It is intended to include any of such substrates with a coating on the material. Thus, where reference is made to an undercoat or photochromic polymeric coating on the surface of a substrate within the present disclosure or claims, such references refer to such coatings as polymeric organic groups. Includes application to coatings on the material itself or on the surface of the substrate (eg, abrasion resistant coatings). As such, the term "base material" includes a base material having a coating on its surface. Such coatings can be any suitable coating (except photochromic coatings), which can be, for example, an abrasion resistant coating (hard coat) (eg, any protective coating), or a substrate thereof. There are, but are not limited to, other coatings that provide one or more additional functional properties (eg, one or more light conditioning functions) for the articles that are part of it.

In a non-limiting embodiment, the substrate is a material that provides a fixed color, a polarizing material or a polarizing layer, or one or more other functional properties within the matrix or on at least a portion of the surface of the substrate. Can have. It is also intended that the substrate may have a light conditioning function within its matrix and may also have a light conditioning function on at least a portion of the surface of the optical substrate. In the latter case, the light conditioning functions within and on the optical substrate complement each other and the photochromic coatings containing the dendritic polymeric acrylates. For example, the substrate matrix can have a fixed color and its surface can have a polarizing material or a polarizing layer.

Photochromic coatings containing dendritic polymeric acrylates may be applied to only a portion of one or more surfaces of the substrate, but are generally applied to the entire surface of at least one surface of the substrate. The amount of photochromic coating applied to the selected surface of the substrate is sufficient to produce a coating that exhibits the desired change in optical density (ΔOD) when the cured coating is exposed to ultraviolet (UV) irradiation. An amount that provides a good amount of photochromic material, i.e. a photochromic amount. In a non-limiting embodiment, the change in optical density measured at 22 ° C (72 ° F) after 30 seconds of UV exposure is at least 0.05, generally at least 0.15, eg at least 0.20. .. In a non-limiting embodiment, the change in optical density after 15 minutes of UV exposure is at least 0.10, generally at least 0.50, eg at least 0.70.

In an alternative non-limiting embodiment, the amount of effective photochromic material used in the photochromic coating ranges from 0.5 to 40.0% by weight based on the total weight of the monomer / resin used to produce the coating. obtain. In general, the concentration of effective photochromic material in the photochromic coating may vary from 1.0 to 30% by weight, generally in the range of 3 to 20% by weight, for example 3 to 10% by weight. Can be a range (relative to the total amount of monomer / resin used to produce the coating). The amount of photochromic material in the coating can range between any combination of these values (including the listed values).

The thickness of the photochromic coating containing the dendritic polymeric acrylate applied to the surface of the hard substrate can be varied. In a non-limiting embodiment, the photochromic coating has a thickness of at least 3 microns. In an alternative non-limiting embodiment, the photochromic coating has a thickness of at least 5 microns, generally at least 10 microns, such as at least 20 or 30 microns. In one non-limiting embodiment, the applied photochromic coating has a thickness of 200 microns or less. In an alternative non-limiting embodiment, the thickness of the applied photochromic coating is 100 microns or less, generally 50 microns or less, for example 40 microns or less. The thickness of the photochromic coating can range between any combination of these values (including the listed values). For example, the thickness of the applied photochromic coating can range from 5 to 50 microns (eg, 10 microns, or 20 to 40 microns). The applied photochromic coating preferably has no cosmetic defects (eg, scratches, holes, stains, crevices, cracks).

Photochromic materials (eg, photochromic dyes / compounds or compositions containing such dyes / compounds) that can be utilized for photochromic coatings are known to those skilled in the art (or later) as inorganic and / or organic photochromic compounds. It is a substance containing such an organic photochromic compound (discovered). The particular photochromic material (eg, compound) selected will vary depending on the final application and the color or hue desired for that application. When multiple photochromic compounds are used in combination, they are generally selected to complement each other to exhibit the desired color or hue.

Organic photochromic compounds typically used in photochromic coatings have at least one activated absorption maximal within the visible spectrum between 300 and 1000 nm (eg, between 400 and 700 nm). Organic photochromic materials are incorporated into coating formulations containing dendritic polymeric acrylates, eg, by dissolution or dispersion, and are colored when activated (eg, when exposed to UV irradiation).

Inorganic photochromic materials generally include microcrystals of silver halide, cadmium halide, and / or copper halide. Generally, the halide material is chloride or bromide. Other inorganic photochromic materials can be prepared by adding europium (II) and / or cerium (III) to mineral glass (eg, soda glass silicate). In a non-limiting embodiment, the inorganic photochromic material is added to the molten glass and formed into particles that are incorporated into the coating composition used to form the polymeric photochromic coating. Such inorganic photochromic materials are described in Kirk Othmer Encyclopedia of Chemical Technology, 4th Edition, Volume 6, pp.322-325. This disclosure is incorporated herein by reference.

Non-limiting examples of organic photochromic compounds that can be used in photochromic coatings include pyran (eg benzopyran), chromen (eg naphthopyran, eg naphtho [1,2-b] pyran, naphtho [2,1-b]. Pyran, spiro-9-fluoreno [1,2-b] pyran, phenanthropyran, quinopyran and indeno-condensed naphthopyran), the disclosure of which is incorporated herein by reference in US Pat. No. 5,645,767. It includes those disclosed in column 1, lines 10 to 12, line 57, and in US Pat. No. 5,658,501, column 1, lines 64 to 13, line 36. Further non-limiting examples of organic photochromic compounds that can be used include oxazines such as benzoxazines, naphthoxazines and spiro (indolin) pyridobenzoxazines. In a further non-limiting embodiment, additional photochromic materials that may be used include, for example, the photochromic metal ditisonate described in US Pat. No. 3,361,706 (eg, mercury dithisonate); the disclosure of which is incorporated herein by reference. U.S. Pat. No. 4,931,220, column 20, lines 5 to 21, line 38, flugide and fludimid (eg, 3-frill and 3-thienylflugide and fludimid); U.S. Patent Application No. 2003 / 0174560 Includes the diarylethene described in paragraphs [0025]-[0086]; and a mixture of any of the aforementioned photochromic materials / compounds.

Further non-limiting examples of organic photochromic compounds, polymerizable photochromic compounds, and complementary photochromic compounds are described in the following US patents: U.S. Pat. No. 5,166,345, Column 3, Lines 36-14, Lines 3; U.S. Pat. No. 5,236,958, Column 1, Lines 45-65; U.S. Pat. No. 5,252,742, Column 1, Lines 45-65; U.S. Pat. No. 5,359,085, column 5, lines 25-19, line 55; U.S. Pat. No. 5,488,119, column 1, lines 29-7, line 65; U.S. Pat. No. 5,821,287, column 3, lines 5 to 11, line 39; U.S. Pat. No. 5,869,658, column 2, lines 5-4, line 37, and column 11, lines 36-57; U.S. Pat. No. 6,113,814, column 2, line 23-column 23, line 29; U.S. Pat. No. 6,153,126, column 2, lines 18-8, line 60; U.S. Pat. No. 6,296,785, Column 2, Lines 47-31, Lines 5; U.S. Pat. No. 6,348,604, Column 3, Lines 26-17, Lines 15; U.S. Pat. No. 6,353,102, column 1, lines 62 to 11, line 64; and U.S. Pat. No. 6,630,597, column 2, lines 24 to 4, line 32, and column 9, lines 3 to 17. The above disclosure is incorporated herein by reference. Furthermore, it is intended that organic photochromic materials such as photochromic pigments and photochromic compounds encapsulated in metal oxides can be used in photochromic coatings. See, for example, the materials described in US Pat. Nos. 4,166,043 and 4,367,170.

The photochromic coating contains at least one photochromic material. In an alternative non-limiting embodiment, the photochromic coating may comprise a mixture of two or more photochromic materials. By using a mixture of photochromic materials, it is possible to obtain a particular activated color (eg, a color close to mid-gray, or a color close to mid-brown). See, for example, U.S. Pat. No. 5,645,767, column 12, lines 66 to 13, line 19, which describes the parameters that define near-middle gray and near-middle brown. Such disclosures are incorporated herein by reference.

Even if compatible hues (eg, pigments) are added to the photochromic coating formulation for medical or fashion reasons (eg, for more aesthetic results). , May be applied to plastic substrates. The particular dye selected can be varied and can vary depending on the needs described above and the outcome to be achieved. In a non-limiting embodiment, the dye complements the color obtained when the photochromic material used is activated (eg, achieves a more natural hue or absorbs a particular wavelength or incident light). Can be selected. In another non-limiting embodiment, the dye may be selected to provide the substrate and / or coating with the desired hue when the photochromic coating is in an unactivated state.

In a further intended non-limiting embodiment, the abrasion resistant coating may be overlaid (eg, may be overlaid) on the photochromic dendritic polymeric acrylate coating. Abrasion resistant coatings (hard coats), especially those containing an organosilane material, are used to protect the surface from abrasion, abrasion and the like. Organosilane-containing abrasion-resistant coatings, often referred to as hardcoats or silane-based hardcoats, are well known in the art and are from a variety of manufacturers (eg, SDC Coatings, Inc. and PPG Industries, Inc.). It is commercially available from Inc.). U.S. Pat. Nos. 4,756,973, which discloses organic silane hard coatings, column 5, lines 1-45, and column 5,462,806, column 1, lines 58-2, lines 8 and line 3 and lines 52. ~ See column 5, line 50. Such disclosures are incorporated herein by reference. See also U.S. Pat. Nos. 4,731,264, 5,134,191, 5,231,156, 6,808,812, and International Patent Application Publication No. 94/20581, which disclose hard coatings.

Other coatings that provide abrasion and scratch resistance (eg, polyfunctional acrylic hard coatings, melamine hard coatings, urethane hard coatings, alkyd coatings, silica sol hard coatings, or other organic or inorganic / Organic hybrid hard coatings) can also be used as abrasion resistant coatings.

In a non-limiting embodiment, the hard coat is based on the following empirical formula X: R¹SiW₃ X [In the formula, R¹Is glycidoxy (C₁~ C₂₀) Alkyl, preferably glycidoxy (C)₁~ C₁₀) Alkyl, more preferably glycidoxy (C)₁~ C₄) Alkyl; W is hydrogen, halogen, hydroxy, C₁~ C₅Alkoxy, C₁~ C₅Alkoxy (C₁~ C₅) Alkoxy, C₁~ C₄Acyloxy, phenoxy, C₁~ C₃Alkyl phenoxy, or C₁~ C₃Alkoxyphenoxy, the halogen of which is bromo, chloro or fluoro], can be prepared from a composition containing 35-95% by weight of at least one organosilane monomer, calculated as a solid. In general, W is hydrogen, halogen, hydroxy, C₁~ C₃Alkoxy, C₁~ C₃Alkoxy (C₁~ C₃) Alkoxy, C₁~ C₂Acyloxy, phenoxy, C₁~ C₂Alkyl phenoxy, or C₁~ C₂Alkoxyphenoxy, the halogen of which is chloro or fluoro. In one non-limiting embodiment, W is hydroxy, C₁~ C₃Alkoxy, C₁~ C₃Alkoxy (C₁~ C₃) Alkoxy, C₁~ C₂Acyloxy, phenoxy, C₁~ C₂Alkyl phenoxy, or C₁~ C₂Alkoxy phenoxy.

Non-limiting examples of silane monomers represented by the general chemical formula X are: glycidoxymethyltriethoxysilane, glycidoxymethyltrimethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyl Triethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxyethyl Trimethoxysilane, β-glycidoxyethyl triethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl Includes triethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltrimethoxysilane, a hydrolyzate of such a silane monomer, and a mixture of such a silane monomer and its hydrolyzate. Is done.

The abrasion resistant coating (hard coat) can be applied to the photochromic coating by a conventional coating method such as spin coating or dip coating. The thickness of the abrasion resistant coating may vary. In one non-limiting embodiment, the thickness of the abrasion resistant coating can be in the range of 0.5-10 microns. Prior to applying a hard coat (eg, an organosilane hard coat), a photochromic coating or a treatment may be applied to the coating to which the hard coat is applied to increase the acceptability to the hard coat and the adhesion to the hard coat. .. For example, it is possible to use the above-mentioned processing such as plasma and corona discharge processing.

In a further non-limiting embodiment, additional coatings (eg, antireflection coatings) may be applied to the hard coat layer. Non-limiting examples of anti-reflective coatings are described in US Pat. No. 6,175,450 and International Patent Publication No. 00/33111.

The present invention will be described in more detail in the examples below, but these examples are intended only by way of illustration, as many adjustments and changes thereof will be apparent to those skilled in the art. In this example, the percentage shall be% by weight unless otherwise specified. If materials such as monomers, catalysts, initiators, etc. are identified by lowercase letters in parentheses in one example and are also used in yet another example, those materials are identified by the same lowercase letters in subsequent examples. ..

In the following examples, a 72 mm flat lens prepared from diethylene glycol bis (allyl carbonate) was used.

(<u style="single">reference</u>Example 1) After the test planar lens is washed with soapy water and dried, oxygen is introduced into the vacuum chamber of the Plasmatech device at a rate of 100 ml / min for 1 minute at a power level of 100 watts using a Plasmatech device. Treated with oxygen plasma. The lens was then rinsed with deionized water and air dried. The photochromic dendritic polyester acrylate coating composition was applied to the plasma treated lens by spin coating (target value of pre-drying weight: 0.18 g), and the coated lens was placed on the conveyor belt of the EYE UV device and the lens was placed. Exposed to ultraviolet light (V sphere) for about 30 seconds It was cured by doing. Table I lists the components of the coating composition and their amounts. The thickness of the photochromic coating was about 30 microns.

<tables num="1"><img id="000007" he="80" wi="139" file="JP5259407B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>(a) NXT-7022 is a dendritic polyester methacrylate prepared by methacrylizing a polyester polyol having 16 terminal hydroxyl groups, the average of which is about 85 to 90% converted to a methacrylate group. Reported by. (b) Antioxidants sold by Ciba-Geigy. (c) FA-711MM hindered amine light stabilizer sold by Hitachi Kasei Kogyo Co., Ltd. (d) A mixture of proportions of naphthopyran photochromic material designed to give the coating a gray hue when activated by UV irradiation. (e) Fluorinated surfactants sold by 3M Company. (f) [Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide] Photoinitiator (Irgacure 819 sold by Ciba-Geigy). (g) Diphenyl (2,4,6-trimethylbenzoylphosphine oxide) photoinitiator sold by Aldrich.

(1) The photochromic material was mixed with N-methylpyrrolidinone. The mixture was stirred at 60 ° C. for about 1 hour. Next, all of the remaining components of the coating composition (except NXT-7022 resin and FC-431) were added and the resulting mixture (solution A) was stirred at room temperature until well mixed. Then, NXT-7022 resin and FC-431 were mixed with Solution A, and the obtained coating composition was stirred until sufficiently mixed.

When the test lens was exposed to ultraviolet light, a color change was observed. When the UV light source was removed, the lens returned to its original transparent state. Two test lenses were tested for photochromic response at 72 ° F (22 ° C) on an optical bench. The average value of the change in optical density value (ΔOD) (for example, the change in optical density from an inactive state or a fading state to an active state or a dark color state) with respect to a lens in 30 seconds is 0.300, and the optical density in 900 seconds. The average value change was 0.765. Average fading speed (fading time-phototop T)_1/2) Is 209 seconds, and the second average fading speed (fading time-second phototopic T)_1/2) Was 743 seconds. The change in optical density (ΔOD) is calculated according to the following equation: ΔOD = log (% Tb /% Ta): where% Tb is the transmittance% in the faded state and% Ta is the activated state. The transmittance is%, and the base of the logarithm is 10. Fading speed (T_1/2) Is the time interval (seconds) until the ΔOD of the activated lens reaches 1/2 of the maximum value of ΔOD after removing the radiation source of the activated radiation. Second fading speed (second T)_1/2) Is the time interval (seconds) until the ΔOD of the activated lens reaches 1/4 of the maximum value of ΔOD after removing the radiation source of the activated radiation.

(<u style="single">reference</u>Example 2) Except that the resin used in the coating composition contains 70% by weight of NXT-7022 dendritic polyester methacrylate and 30% by weight of bisphenol A ethoxylate dimethacrylate having about 30 ethoxy sites per molecule.<u style="single">reference</u>Followed the procedure in Example 1.

When the test lens was exposed to ultraviolet light, a color change was observed. When the UV light source was removed, the lens returned to its original transparent state. The test lens was tested for photochromic response at 72 ° F (22 ° C) on an optical bench. The average value of the change in optical density value (ΔOD) in 30 seconds with respect to the lens was 0.462, and the average value of the change in optical density value in 900 seconds was 0.717. Average fading speed (fading time-phototop T)_1/2) Is 57 seconds, and the second average fading speed (fading time-second phototopic T)_1/2) Was 159 seconds.

(Example 3) Except that the resin used in the coating composition contains 50% by weight of NXT-7022 dendritic polyester methacrylate and 50% by weight of bisphenol A ethoxylate dimethacrylate having about 30 ethoxy sites per molecule.<u style="single">reference</u>Followed the procedure in Example 1. The test lens was tested for photochromic response at 72 ° F (22 ° C) on an optical bench. The average value of the change in optical density value (ΔOD) in 30 seconds with respect to the lens was 0.570, and the average value of the change in optical density value in 900 seconds was 0.744. Average fading speed (fading time-phototop T)_1/2) Is 37 seconds, the second average fading speed (fading time-second phototop T)_1/2) Was 86 seconds.

(Example 4) Except that the resin used in the coating composition contains 30% by weight of NXT-7022 dendritic polyester methacrylate and 70% by weight of bisphenol A ethoxylate dimethacrylate with about 30 ethoxy sites per molecule.<u style="single">reference</u>Followed the procedure in Example 1. The test lens was tested for photochromic response at 72 ° F (22 ° C) on an optical bench. The average value of the change in optical density value (ΔOD) in 30 seconds with respect to the lens was 0.601, and the average value of the change in optical density value in 900 seconds was 0.707. Average fading speed (fading time-phototop T)_1/2) Is 28 seconds, the second average fading speed (fading time-second phototopic T)_1/2) Was 60 seconds.

(<u style="single">reference</u>Example 5) Except for using the coating compositions listed in Table II<u style="single">reference</u>Followed the procedure in Example 1.

<tables num="2"><img id="000008" he="79" wi="139" file="JP5259407B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>(h) PRO-5249 is a 50/50 blend of neopentyl glycol-2-propoxylated diacrylate and dendritic polyester acrylate by its supplier, where about 13 of the 16 terminal hydroxyl groups. It is reported that the individual is acrylicized. (i) Dimethacrylate of PC-1122 (aliphatic polycarbonate diol reported by supplier (Stahl) to be polyhexamethylene dicarbonate) by reaction of diol with isocyanate ethyl methacrylate. (j) TINUVIN-622 hindered amine light stabilizer sold by Ciba-Geigy (k) A mixture of proportions of naphthopyran photochromic material designed to give the coating a gray hue when activated by UV irradiation.

The test lens was tested for photochromic response at 72 ° F (22 ° C) on an optical bench. The average value of the change in optical density value (ΔOD) in 30 seconds with respect to the lens was 0.506, and the average value of the change in optical density value in 900 seconds was 0.789. Average fading speed (fading time-phototop T)_1/2) Is 79 seconds, and the second average fading speed (fading time-second phototopic T)_1/2) Was 233 seconds.

(<u style="single">reference</u>Example 6) Except that the resin used in the coating composition contains 45% by weight PRO-5249 and 55% by weight PC-1122DMA.<u style="single">reference</u>Followed the procedure in Example 5. The test lens was tested for photochromic response at 72 ° F (22 ° C) on an optical bench. The average change in optical density (ΔOD) at 30 seconds for the lens was 0.542; the average change in optical density at 900 seconds was 0.794. Average fading speed (fading time-phototop T)_1/2) Is 67 seconds, and the second average fading speed (fading time-second phototopic T)_1/2) Was 190 seconds.

In the above, the present invention has been described with reference to the specific details of the specific embodiment, but such details extend the scope of the present invention except when it is included in the appended claims. It is not intended to be considered limiting.