HK1073126B - Photochromic polymerizable compositions - Google Patents

Description

Photochromic polymerizable compositions

Reference to related applications

This application claims priority to provisional application No. 60/335,871 filed on.11/1/2001.

Technical Field

The present invention relates to a photochromic composition comprising at least one polymerizable material and a photochromic amount of at least one photochromic compound. The polymerizable composition may optionally also contain other copolymerizable monomers. The photochromic compound can be added to the composition prior to polymerization or after the polymer is formed. The invention also relates to a photochromic polymer and a photochromic article.

Background

Photochromism is a phenomenon that involves the reversible change in color of a photochromic compound, or article containing the compound, upon exposure to light containing ultraviolet light, and the reversion to the original color when the ultraviolet light irradiation is stopped. The light irradiation source containing ultraviolet rays includes, for example, sunlight and light of a mercury lamp. Stopping the ultraviolet radiation can be accomplished, for example, by placing the photochromic compound or article in the dark or by removing the ultraviolet radiation source (e.g., by filtering).

The reversible transition in color exhibited by different types of photochromic compounds, namely: the general mechanism of absorption spectrum changes in the visible (400-700nm) range has been described and classified. See John C.Crano, "Chromogenic Materials (Photochromic)",Kirk-Othmer Encyclopedia of Chemical Techologyfourth edition 1993, page 321-332. For most conventional classes of photochromic compounds, e.g., indole spiropyrans and indole spirooxazines, the general mechanism involves an electrocyclic mechanism. When exposed to activating radiation, these compounds switch from a colorless closed ring compound to a colored open ring species. In contrast, the colored form of fulgide photochromic compounds is produced by an electrocyclic mechanism involving a shift from a colorless open-ring form to a colored closed-ring form.

Among the above electrical cyclization mechanisms, photochromic compounds require an environment in which they can undergo reversible transformations. In a solid polymer matrix, the rate of the activated photochromic process, namely: color formation, or darkening, fading, occurs, i.e.: return to the original or colorless state is believed to be dependent upon empty columns in the polymer matrix. The empty columns of the polymer matrix depend on the flexibility of the segment of the polymer environment around the photochromic compound, i.e.: local variability or local viscosity of the matrix containing the segment. See Claus D.Eisenbach, "New concept of photochromism in bulk polymers", photographic science and engineering, 1979, pp 183-190. According to the reports of Claus d. eisenbach, one of the major obstacles to the large-scale commercial application of photochromic systems is the slow rate of photochromic activation and discoloration in solid polymer matrices.

Recently, photochromic plastic materials have been the subject of much attention, in part because of their ability to provide weight advantages over eyeglasses made of glass. In addition, for vehicles, such as automobiles and airplanes, photochromic transparency has attracted interest due to the potential security features it provides.

In addition to the slow activation rate and discoloration of photochromic compounds in polymer matrices, a further disadvantage of the widespread commercial use of organic photochromic compounds in combination with plastic materials is that they lose the ability to exhibit a reversible change in color due to repeated exposure to ultraviolet light (UV) for extended periods of time. This phenomenon is believed to be the result of irreversible decomposition of the organic photochromic compound, and is referred to as fatigue.

While some progress has been made in enhancing fatigue resistance and improving the performance of photochromic materials, further improvements, even small ones, are still needed in fatigue resistance and/or in improving the performance of photochromic polymeric materials. Accordingly, efforts continue to be made to achieve this advance.

Despite the photochromic compounds and polymerizable compositions, such as: the combined use of (meth) acrylates is known, but the use of the polymerizable composition with photochromic compounds of the present invention is not disclosed.

Disclosure of Invention

In one non-limiting embodiment of the present invention, a polymerizable composition is provided that includes a photochromic amount of at least one photochromic compound, at least one material having at least one carbonate group and at least one hydroxyl group, and at least one monoisocyanate containing material having at least one unsaturated group. The polymerizable composition may optionally further comprise other copolymerizable monomers.

In a further non-limiting embodiment, the polymerizable composition of the present invention can be adapted to reduce the percent optical fatigue of the photochromic compound in the accelerated aging photochromic percent optical fatigue test (AWPPPF test) when at least partially cured. The AWPPPF test is described in example 15 of the present application. In this test, the polymerizable composition of the present invention and other polymerizable compositions were tested for photochromic properties and fatigue as components of a methacrylic coating composition.

In another non-limiting embodiment of the present invention, a polymerizable composition is provided that comprises the reaction product of component (a) a polyol comprising at least one carbonate group and an isocyanate comprising one reactive isocyanate group and at least one polymerizable double bond; optionally component (b) at least one other monomer copolymerizable with component (a); and component (c) a photochromic amount of at least one photochromic compound.

In one non-limiting embodiment, it has been unexpectedly found that when the polymerizable compositions of the present invention are used in polymerizable photochromic compositions, e.g., methacrylic coating compositions, the percent fatigue of the photochromic compound is reduced as described in the AWPPPF test described in example 15 herein. It has also been found that the polymerizable compositions of the present invention listed in the AWPPPF test described above have a lower percentage of fatigue of photochromic compounds compared to polycarbonate-based dimethacrylate monomers that do not contain urethane groups.

In various non-limiting embodiments of the present invention, the nature of optional component (b) is not critical, so long as it is copolymerizable with the polymerizable compositions of the present invention. As the present invention relates to the photochromic polymerizable compositions illustrated and claimed herein, any copolymerizable monomer can be used.

In one non-limiting embodiment, the copolymerizable monomer of component (b) may be selected from:

(a) a radically polymerizable monomer represented by the following formula:

wherein R is₈Being a polyvalent residue of a polyol, R₅Is hydrogen or methyl, i is an integer from 2 to 6, X is a radical selected from the group consisting of linear or branched alkylene, linear or branched polyoxyalkylene, cyclic alkylene, phenylene, polyol or C₁-C₄A divalent bonding group of the alkyl-substituted phenylene group of (a);

(b) a radically polymerizable monomer represented by the following formula:

wherein m and n are integers each independently selected from 0 to 6, the sum of m and n is 0 to 6, R₉And R₁₀Each independently selected from hydrogen or methyl, R₁₁And R₁₂Each independently selected from hydrogen or C₁-C₄B is selected from the group consisting of linear or branched alkylene, phenylene, C₁-C₉Or a divalent bonding group of a group represented by the formula:

wherein R is₁₅And R₁₆Are each independently selected from C₁-C₄P and q are integers each independently selected from 0 to 4,represents a divalent phenyl group or a divalent cyclohexyl group when When it is a divalent phenyl group, D is-O-, -S-, -S (O)₂)-、-C(O)-、-CH₂-、-CH＝CH-、-C(CH₃)₂-、-C(CH₃)(C₆H₅) -, orWhen in useWhen it is a divalent cyclohexyl group, D is-O-, -S-, -CH₂-or-C (CH)₃)₂-；

(c) A radically polymerizable monomer represented by the following formula:

wherein o and u are each independently selected from a positive number, the sum of o and u is from 7 to 70, R₉、R₁₀、R₁₁、R₁₂And B is as defined above;

(d) a radically polymerizable monomer represented by the following formula:

wherein R is₅、R₈And R₁₁D is a number selected from 0 to 20, j is a number selected from 3 to 6;

(e) a reaction product of a polycarbonate polyol chloroformate and a hydroxy (meth) acrylate;

(f) a reaction product of a polycarbonate polyol and (meth) acryloyl chloride;

(g) monoethylenically unsaturated, free-radically polymerizable monomers;

(h) a free radically polymerizable allyl-functional monomer having at least two allyl groups, with the proviso that the allyl-functional monomer is used in an amount of not more than 5 weight percent based on the total weight of the monomers; or

(i) Mixtures of the above monomers.

In various non-limiting embodiments, the polymerizable compositions of the present invention can be used to prepare photochromic polymers in which photochromic compounds can be added to the at least partially cured polymer prior to polymerization, or a combination of these methods.

It is noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the content of a referent is expressly and unequivocally limited to the one referent.

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

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

Detailed Description

The term "at least partially cured polymer" refers to a polymerizable composition in which the curable or cross-linked components are at least partially cured, cross-linked, and/or reacted. In certain non-limiting embodiments of the invention, the extent of the components that are reacted is wide, e.g., 5% to 100% of all possible curing, crosslinking, and/or reacting components.

The related applications, patents and articles describing methods for preparing monomers, polymers and photochromic compounds listed herein in columns or rows or detailed description are hereby incorporated by reference into this application.

The term "polyol" is defined herein as a polyhydric alcohol having 2 or more hydroxyl groups, but substantially no carbonate groups unless otherwise specified. The polyol residue or group derived from the polyol is the moiety remaining after removal of the hydroxyl group(s) from the polyol. The term "alkylene", when preceded by a linear, i.e.: straight chain, or branched, refers to hydrocarbon groups having 2 to 20 carbon atoms. The term "alkylene oxide" is defined herein as a hydrocarbon group having 2 to 4 carbon atoms and 1 oxygen atom. By "oxyalkylene" it is meant herein that the number of oxyalkylene groups included in the formula is included in a specified range, e.g., an integer or number from 0 to 6, or a fractional number such as 1.1 or 5.9. The term "cyclic alkylene" is defined herein as a cyclic hydrocarbon group having 3 to 7 carbon atoms. The term "(meth) acryloyl" is defined as acryloyl, methacryloyl, or a combination of acryloyl and methacryloyl. The term "(meth) acrylate" is defined herein as acrylate, methacrylate, or a combination of acrylate and methacrylate. The term "(meth) acrylic" is defined herein as acrylic, methacrylic or a combination of acrylic and methacrylic groups.

In the description of component (a) and component (b), like letters and like terms mean the same unless otherwise specified.

In one non-limiting embodiment, the polymerizable composition of the present invention is the reaction product of the following reactants: at least one material containing at least one carbonate group and at least one hydroxyl group, such as a carbonate group containing alcohol or polyol or a (meth) acrylic monomeric material containing at least one carbonate and at least one hydroxyl group; at least one substance containing a monoisocyanate having at least one unsaturated group, such as a product of a reaction of a (meth) acrylic monomer material containing a vinyl ether group with an isocyanic acid; and a photochromic amount of at least one photochromic compound.

In another non-limiting embodiment, component (a) is the reaction product of an isocyanate containing one reactive isocyanate group and at least one polymerizable double bond and a polyol containing at least one carbonate group which may be represented by the formula:

wherein R' is a polyol residue containing at least one carbonate group, R₅Is hydrogen or methyl, E is-NH-; x is a radical selected from the group consisting of linear or branched alkylene, linear or branched polyoxyalkylene, cyclic alkylene, phenylene, polyol or C₁-C₄I is an integer of 2 to 6. In another non-limiting embodiment, R' is a polyol residue containing at least two carbonate groups.

In one non-limiting embodiment, the polycarbonate polyol of component (a) can be represented by the formula:

wherein R is₆And R₇May be the same or different and are each independently selected from divalent straight or branched chain alkylene, cyclic alkylene or divalent C₆-C₁₅One of the aryl groups, for example, 2, 2-diphenylenepropane, a is an integer from 1 to 20.

In another non-limiting embodiment, polycarbonate polyols of the above general formula, as described in U.S. Pat. No. 4,5,266,551, may be formed by reacting at least one bis (chloroformate) with at least one polyol, such as a diol. One of these components may be in excess to limit and control the molecular weight of the final polycarbonate polyol. As shown in the following non-limiting polycarbonate preparation scheme, the diol is in excess and forms end groups.

Polycarbonate manufacturing process

Examples of bis (chloroformates) useful in the above scheme include: monoethylene glycol bis (chloroformate), diethylene glycol bis (chloroformate), propylene glycol bis (chloroformate), butanediol bis (chloroformate), hexanediol bis (chloroformate), neopentyl glycol bis (chloroformate), bisphenol a bis (chloroformate), or a mixture thereof, but is not limited thereto.

Examples of polyols that can be used in the above preparation scheme include: bisphenol A, trimethylolethane, trimethylolpropane, ditrimethylolpropane dimethylolpropionic acid, ethylene glycol, propylene glycol, 1, 3-propanediol, 2-dimethyl-1, 3-propanediol, 1, 2-butanediol, 1, 4-butanediol, 1, 3-butanediol, 1, 5-pentanediol, 2, 4-pentanediol, 2, 4-trimethyl-1, 3-pentanediol, 2-methyl-1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, 2, 5-hexanediol, 2-ethyl-1, 3-hexanediol, 1, 4-cyclohexanediol, 1, 7-heptanediol, 2, 4-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 2-dimethyl-3-hydroxypropyl-2, 2-dimethyl-3-hydroxypropionate, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1, 4-cyclohexanedimethanol, 1, 2-bis (hydroxymethyl) cyclohexane, 1, 2-bis (hydroxyethyl) cyclohexane, an alkoxylation product of 1 mole of 2, 2-bis (4-hydroxyphenyl) propane (i.e., bisphenol A) with 2 to 10 moles of ethylene oxide, propylene oxide or a mixture thereof, poly (butylene oxide) diol or a mixture thereof, but is not limited thereto.

In certain non-limiting embodiments, the above materials may be used in combination to form different compositions, chain lengths, and end groups of the polycarbonate polyol. For example, the polyol can have terminal aliphatic hydroxyl groups (e.g., diethylene glycol groups), phenolic terminal groups (e.g., bisphenol a groups), or mixtures of these terminal hydroxyl groups.

In various non-limiting embodiments, polycarbonate polyols, and materials containing at least one carbonate group and at least one hydroxyl group, can be prepared by transesterification of dialkyl, diaryl, or alkylene carbonates with polyols, as described in U.S. Pat. Nos. 4,131,731, 4,160,853, 4,891,421, and 5,143,997. Other examples of materials containing carbonate and hydroxyl groups include products prepared by the following methods: by reaction of a polyol and phosgene as described in US4,533,729; by reaction of a polycarbonate polyol and an anhydride or dicarboxylic acid, as described in U.S. Pat. No. 5,527,879. Examples of commercially available products include: RAVECARB available from EniChem Synthesis Milano^®Polycarbonate diols of the 102-108 series and PC 1122 commercially available from Stahl, USA, but is not limited thereto.

In one non-limiting embodiment, the monoisocyanate used to prepare the polymerizable composition of the present invention has primary, secondary or tertiary isocyanate groups, also referred to as reactive isocyanate groups, and at least one unsaturated group selected from allyl, (meth) acrylic, vinyl, or mixtures thereof. In another non-limiting embodiment, the unsaturated group is a group having a polymerizable double bond selected from (meth) acrylic groups.

In one series of non-limiting embodiments, the isocyanates of component (a) and monoisocyanate species containing at least one unsaturated group can be:

(1) an isocyanate represented by the formula:

CH₂＝C(R₅)-C(O)OX-N＝C＝O

wherein R is₅And X is as described above;

(2) m-isopropenyl-alpha, alpha-dimethylbenzyl isocyanate;

(3) the reaction product of at least one acrylic functional monomer containing one vinyl ether group and isocyanic acid; or

(4) Mixtures thereof.

In one non-limiting embodiment, the isocyanate that may be used as a reactive agent to form component (a) is a material having one reactive isocyanate group and at least one polymerizable double bond. A non-limiting example of such a compound is isocyanatoethyl methacrylate. By way of non-limiting illustration, processes for preparing such compounds have been described in Thomas, Mary r, entitled "isocyanatoethyl methacrylate: a heterofunctional monomer "of polyurethane and vinyl polymer systems, an advance in organic coatings and polymer science, was disclosed in 1982, Vol.46, p.506-513. Non-limiting methods for preparing m-isopropenyl-alpha, alpha-dimethylbenzyl isocyanate are disclosed in US4,377,530, US4,379,767 and US4,439,616. By way of further non-limiting illustration, methods for preparing reaction products of acrylic functional monomers containing one vinyl ether group with isocyanic acid, such as, for example, 1- (2-methacryloyloxyethoxy) ethyl isocyanate, have been disclosed in Hoover, F.W., et al, "isocyanic acid chemistry, II. reaction with α, β -unsaturated ethers", J.Organic Chemie, 1963, Vol.28, p.2082-2085.

In a further non-limiting embodiment, the isocyanate of component (a), as defined herein, may comprise a "modified" or "unmodified" isocyanate having "free", "blocked" or partially blocked isocyanate groups. The isocyanate-containing compound may be selected from fatsAromatic, cycloaliphatic, heterocyclic isocyanates or mixtures thereof. The term "modified" here means that the above-mentioned isocyanate-containing compounds are modified by known methods to introduce biuret, urea, carbodiimide, urethane or isocyanurate groups. Other methods for modifying isocyanates are described inUllmann's encyclopedia of chemical industryFifth edition, 1989, volume A14, page 611 and 625, and U.S. Pat. No. 2, line 63 to column 3, line 31, U.S. Pat. No. 3, 4,442,145.

The free isocyanate groups are unstable, i.e.: the isocyanate groups will react with water or compounds containing active hydrogen atoms. In order to provide stable and storable isocyanates and/or isocyanate-containing compounds, the NCO groups can be blocked with certain selected organic compounds which render the isocyanate groups chemically unreactive at room temperature with active hydrogen compounds. When heated to higher temperatures, e.g., 90-200 ℃, the blocked isocyanate releases the blocking agent and reacts in the same manner as the original unblocked or free isocyanate.

In one non-limiting embodiment, the isocyanate may be fully blocked as described in U.S. Pat. No. 3,984,299 column 1 lines 1-68, column 2 and column 3 lines 1-15; or as described in U.S. patent No. 3,947,338 at column 2, line 65 to column 4, line 30; is partially blocked and reacts with the polymer backbone. As used herein, NCO in the NCO: OH ratio refers to the free or reactive isocyanate in the free isocyanate-containing compound and the blocked or partially blocked isocyanate-containing compound after release of the blocking agent. In some cases, it is not possible to remove all of the blocking agent. In these cases, more blocked isocyanate-containing compound may be used to achieve the desired free NCO level.

In another non-limiting embodiment, the isocyanate-containing compound is selected from the group consisting of modified or unmodified aliphatic isocyanates, cycloaliphatic isocyanates, aromatic isocyanates, partially blocked aliphatic isocyanates, partially blocked cycloaliphatic isocyanates, partially blocked aromatic isocyanates, or mixtures thereof. In another non-limiting embodiment, the isocyanate is selected from modified forms of aliphatic isocyanates, cycloaliphatic isocyanates, aromatic isocyanates, or mixtures thereof. In a further non-limiting embodiment, the isocyanate component is an unmodified aliphatic isocyanate.

Generally, the compounds used to block the isocyanates are certain organic compounds having active hydrogen atoms. In one non-limiting embodiment, examples include volatile alcohol, amine, acid ester, epsilon-caprolactam, triazole, pyrazole, and ketoxime compounds. In another non-limiting embodiment, the blocking compound may be selected from the group consisting of methanol, t-butanol, phenol, cresol, nonylphenol, diisopropylamine, diethyl malonate, ethyl acetoacetate, epsilon-caprolactam, 3-aminotriazole, 1, 2, 4-triazole, pyrazole, 3, 5-dimethylpyrazole, acetoxime, methyl amyl ketoxime, methyl ethyl ketoxime, or mixtures thereof. In a further non-limiting embodiment, the blocking compound is selected from methanol, diisopropylamine, diethyl malonate, ethyl acetoacetate, 1, 2, 4-triazole, methyl ethyl ketoxime, acetoxime or mixtures thereof. In still further non-limiting embodiments, the blocking compound is methanol, diisopropylamine, methyl ethyl ketoxime, 1, 2, 4-triazole, or a mixture thereof.

In one non-limiting embodiment, the ratio of monoisocyanate-containing material having at least one unsaturated group to material containing at least one carbonate group and at least one hydroxyl group is in the range of 1: 1 to 1: 7, such as 1: 2 to 1: 6 or 1: 2 to 1: 5. The NCO: OH ratio can range between any combination of these values within the ranges set forth above, for example, from 1: 1.5 to 1: 6.9.

In another non-limiting embodiment, the molecular weight distribution of the reaction product of at least one material comprising at least one carbonate group and at least one hydroxyl group and at least one monoisocyanate comprising a material having at least one unsaturated group, e.g., component (a), is broad. It can range from the minimum number of molecular weights of the ingredients used to form the reaction product, about 200 grams per mole, to macromolecular polymeric species having a number average molecular weight of 200,000 based on polystyrene standards. For example, the molecular weight may be in the range of 500 to 17,500 number average molecular weight based on polyethylene glycol standards, or 1500 to 100,000 number average molecular weight based on polystyrene standards. The molecular weight of the reaction product may range from any combination of these values, for example, from a molecular weight of 250 grams per mole to a number average molecular weight of 150,000. In one contemplated non-limiting embodiment, component (a) has a molecular weight of greater than 2,000 number average molecular weight based on polystyrene standards.

In a non-limiting series of embodiments, component (a) may be present in the composition in an amount ranging from 5 to 100 weight percent, based on the total weight of the polymerizable non-photochromic component, for example. Component (a) may be present in the polymerizable compositions of the present invention in an amount of at least 5 weight percent, for example, at least 20 weight percent, or at least 30 weight percent, based on the total weight of the polymerizable non-photochromic component. Component (a) may be present in the polymerizable composition in an amount of less than 95 weight percent by weight, for example, less than 75 weight percent by weight, or less than 50 weight percent by weight, with weight percents being based on the total weight of the polymerizable non-photochromic component. The amount of component (a) monomer that may be present in the polymerizable composition of the present invention may vary within any combination of these upper and lower values within the ranges set forth above, for example, from 6 to 99 weight percent.

In another series of non-limiting embodiments, the amount of optional copolymerizable monomer component (b) monomer that can be present in the compositions of the present invention can range widely. The copolymerizable monomer may be present in the polymerizable composition in an amount of at least 5 weight percent by weight, for example, at least 25 weight percent by weight, or at least 50 weight percent by weight, with these weight percents being based on the total weight of the polymerizable non-photochromic component. The copolymerizable monomer may be present in the polymerizable composition in an amount of less than 95 weight percent by weight, for example, less than 80 weight percent by weight, or less than 70 weight percent by weight, based on the total weight of the polymerizable non-photochromic component. The amount of copolymerizable monomer that can be present in the polymerizable composition can vary within any combination of these upper and lower values within the ranges set forth above, e.g., from 10 to 90 weight percent. The weight percentages of component (a) and component (b) make up 100 wt% based on the total weight of the polymerizable non-photochromic component.

In one non-limiting embodiment, the first copolymerizable monomer of the polymerizable organic composition of the present invention may be a carbonate of a (meth) acryloyl terminated linear or branched aliphatic polyol, cycloaliphatic polyol, aromatic polyol, or ester group containing polyol, for example, an aliphatic diol bis ((meth) acryloyl carbonate) monomer, an alkylene bisphenol bis ((meth) acryloyl carbonate) monomer, or a polyester bis ((meth) acryloyl carbonate) monomer. Non-limiting methods for preparing the first monomer are described in U.S. Pat. No. 5,5,965,680.

With reference to the above general formula, R₈Is a polyvalent residue of a polyol which may be an aliphatic polyol, a cycloaliphatic polyol, an aromatic polyol or a polyol containing ester groups containing at least 2 hydroxyl groups, e.g., 3, 4,5 or 6 hydroxyl groups. The polyhydric alcohol having 2 or more hydroxyl groups includes, for example, glycerin, trimethylolpropane, trimethylolethane, ditrimethylolpropane, ditrimethylolethane, pentaerythritol and dipentaerythritol. X is a divalent bonding group as defined above, R₅Is hydrogen or methyl. In one non-limiting embodiment, R₅Is methyl, and the letter i is an integer from 2 to 6. In another non-limiting embodiment, i is 2.

In a series of non-In a limiting embodiment, R₈The polyol being a residue contains 2 hydroxyl groups, i.e.: diols, such as ethylene glycol or bisphenols. The aliphatic polyols may be straight or branched chain and contain 2 to 20 carbon atoms. In one non-limiting embodiment, the aliphatic polyol is an alkylene glycol having 2 to 4 carbon atoms, for example, ethylene glycol, propylene glycol, butylene glycol, and/or poly (C)₂-C₄) Alkylene glycols, such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol, and the like.

In a further non-limiting embodiment, R₈The polyol which is a residue may also be selected from 1, 3-benzenediol, 1, 4-benzenediol, hydroxyquinone bis (2-hydroxyethyl) ether, or a bisphenol represented by the formula:

wherein R is₁₃And R₁₄Are each independently selected from C₁-C₄One of alkyl, chloro or bromo; p and q are each independently an integer from 0 to 4; a-is selected from-O-, -S (O)₂)-、-C(O)-、-CH₂-、-CH＝CH-、-C(CH₃)₂-、-C(CH₃)(C₆H₅) -orOne of them.

In another further non-limiting embodiment, R₈Cycloaliphatic polyols which may be selected include: 1, 2-, 1, 3-or 1, 4-dimethylolcyclohexane, or bisphenol hydrogenation products, such as bicyclohexanol, described further herein. R₈A non-limiting example of bicyclohexanol that may be selected is 4, 4' -isopropylidenedicyclohexanol.

In another non-limiting embodiment of the invention, R₈The polyol being a residue selected from alkylene glycols, poly (C)₂-C₄) Alkylene glycol, glycerol, 1, 3-benzenediol, 1, 4-benzenediol, hydroxyquinone bis (2-hydroxyethyl) ether glycol, or mixtures thereof. In one non-limiting embodiment, R₈The polyhydric alcohol being a residue is selected from alkylene glycols, e.g. ethylene glycol, or poly (C)₂-C₄) Alkylene glycols, for example, diethylene glycol.

Examples of the polyol ((meth) acryloyl carbonate) monomer that may be selected for the first copolymerizable monomer (a) include: ethylene glycol bis ((methacryloxy) ethylene carbonate), ethylene glycol bis ((acryloxy) ethylene carbonate), diethylene glycol bis ((methacryloxy) ethylene carbonate), diethylene glycol bis ((acryloxy) ethylene carbonate), triethylene glycol bis ((methacryloxy) ethylene carbonate), triethylene glycol bis ((acryloxy) ethylene carbonate), propylene glycol bis ((methacryloxy) ethylene carbonate), 1, 3-propylene glycol bis ((acryloxy) ethylene carbonate), 1, 3-butylene glycol bis ((methacryloxy) ethylene carbonate), 1, 2-and 1, 3-propanetriol bis ((methacryloxy) ethylene carbonate), 1, 2-and 1, 3-propanetriol bis ((acryloyloxy) ethylene carbonate), 1, 4-butanediol bis ((methacryloxy) ethylene carbonate), 1, 4-butanediol bis ((acryloyloxy) ethylene carbonate), dipropylene glycol bis ((methacryloxy) ethylene carbonate), dipropylene glycol bis ((acryloyloxy) ethylene carbonate), trimethylene glycol bis ((methacryloxy) ethylene carbonate), trimethylene glycol bis ((acryloyloxy) ethylene carbonate), pentamethyleneglycol bis ((methacryloxy) ethylene carbonate), pentamethyleneglycol bis ((acryloyloxy) ethylene carbonate), 1, 3-and 1, 4-benzenediol bis ((methacryloxy) ethylene carbonate), 1, 3-and 1, 4-benzenediol bis ((acryloyloxy) ethylene carbonate), hydroxyquinone bis (2-hydroxyethyl) ether bis ((methacryloyloxy) ethylene carbonate), hydroxyquinone bis (2-hydroxyethyl) ether bis ((acryloyloxy) ethylene carbonate), isopropylidene bisphenol bis ((methacryloyloxy) ethylene carbonate), isopropylidene bisphenol bis ((acryloyloxy) ethylene carbonate), diethylene glycol bis ((methacryloyloxy) 2-methyl-ethylene carbonate), diethylene glycol bis ((methacryloyloxy) 1, 4-cyclohexylene carbonate), diethylene glycol bis ((methacryloyloxy) 1, 4-phenylene carbonate), diethylene glycol bis ((methacryloyloxy) 2, 5-dimethyl-1, 3-phenylene carbonate), or mixtures thereof, but not limited thereto.

In a further non-limiting embodiment, R₈The polyol that is a residue is a polyol that includes ester groups. Such polyols are generally known and may have a number average molecular weight in the range of 200-10,000. They may be prepared by conventional techniques known in the art using low molecular weight diols, which are diols having a molecular weight of 500 grams per mole or less, triols and polyols (optionally in combination with monohydric alcohols), reacted with polycarboxylic acids. Non-limiting examples of polycarboxylic acids include: phthalic acid, isophthalic acid, terephthalic acid, 1, 2, 4-trimellitic acid, tetrahydrophthalic acid, adipic acid, succinic acid, glutaric acid, fumaric acid, or mixtures thereof. Anhydrides present in the above acids may also be used and are included within the term "polycarboxylic acids".

In another further non-limiting embodiment, certain materials that react in a similar manner to acids to form polyester polyols may also be used. These include lactones such as: caprolactone, propiolactone and butyrolactone; and hydroxy acids such as hydroxycaproic acid and dimethylolpropionic acid. If a triol or polyol is used, a monocarboxylic acid, such as acetic acid and/or benzoic acid, may be used to prepare the polyester polyol, which is desirable for some purposes. Moreover, the polyester polyols in the present application should be understood to include polyester polyols modified with fatty acids or fatty acid glyceride oils (i.e., conventional alkyd polyols containing such modifications). Non-limiting examples of other polyester polyols that may be used are those prepared by alkylene oxides such as: ethylene oxide, propylene oxide, and the like, as well as glycidyl esters of branched alkane carboxylic acids, are reacted with methacrylic acid to form the corresponding ester-prepared polyester polyols.

In one non-limiting embodiment, when R₈In the case of the residue of an ester group-containing polyol, the polyol in which the residue is taken may be represented by the following formula:

R₁-(Y-(C(O)(-CR₂R₃)_h-CHR₄-O)_t-H)_y

wherein: y is-O-or-NR-, R is hydrogen or C₁-C₁₂An alkyl group; r₁Is an initiator-derived organic radical. Initiators are compounds having at least one active hydrogen which are capable, with or without the aid of a catalyst, of opening the lactone ring and adding it as an open chain without condensation to form water. Non-limiting examples of initiators include monofunctional initiators such as alcohols and amines, and multifunctional initiators such as polyols, polyamines, aminoalcohols, and vinyl polymers and amides, sulfonamides, hydrazones, semicarbazones, oximes, polycarboxylic acids, hydroxycarboxylic acids, and aminocarboxylic acids. R₂、R₃And R₄Each independently selected from hydrogen and C₁-C₁₂Alkyl of (C)₅-C₆Cycloalkyl of, C₁-C₆Alkoxy, benzyl or phenyl with the proviso that R₂、R₃And R₄At least h +2 of the total number is hydrogen. For example, when the starting material is butyrolactone (C)₄H₆O₂) When h is 2 and at least 4, in fact R₂、R₃And R₄5 of the total are hydrogen. The letter h is an integer selected from 1 to 6; t is an integer selected from 1 to 100; y is an integer selected from 2 to 6.

In another non-limiting embodiment, the polyol containing ester groups is the reaction product of a diol initiator and a lactone, i.e.: a polylactone diol. The diol of the polylactone diol may be selected from the group consisting of linear or branched aliphatic diols having 2 to 20 carbon atoms, poly (C)₂-C₄) Alkylene glycols, cycloaliphatic diols having 5 to 8 carbon atoms in the ring, monocyclic aromatic diols, bisphenols, hydrogenated bisphenols, or mixtures thereof.

Examples of linear or branched aliphatic diols having 2 to 20 carbon atoms that can be used to prepare the polylactone diols include R₈A diol which is a residue, but is not limited thereto. Non-limiting examples of such diols include: ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 2-and 2, 3-butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, dodecanediol, tridecanediol, tetradecanediol, pentadecanediol, hexadecanediol, heptadecanediol, octadecanediol, nonadecanediol and eicosanediol. Poly (C)₂-C₄) Examples of alkylene glycols include: di-, tri-, tetra-, penta-, and more vicinal glycols; di-, tri-, tetra-, penta-, and more linked propylene glycol; and di-, tri-, tetra-, penta-, and more linked butanediols, but is not limited thereto.

Cycloaliphatic diols having 5 to 8 carbon atoms which can be used to prepare the polylactone diols include: but are not limited to, cycloaliphatic diols such as those previously described herein, cyclopentyl diol, cyclohexyl dimethanol, cycloheptyl diol, and cyclooctyl diol. Examples of monocyclic aromatic diols that can be used to prepare polylactone diols include: benzene diols such as 1, 2-dihydroxybenzene and 1, 3-dihydroxybenzene; c₁-C₄Alkyl-substituted benzenediols, for example 4-tert-butyl-phenyl-1, 2-diol, 4-methyl-phenyl-1, 2-diol, 3-tert-butyl-5-methyl-phenyl-1, 2-diol and 3, 4,5, 6-tetramethyl-phenyl-1, 2-diol; halogenated benzene diols, such as 3, 5-dichlorophenyl-1, 2-diol, 3, 4,5, 6-tetrabromo-phenyl-1, 2-diol and 3, 4, 5-trichloro-phenyl-1, 2-diol; and C₁-C₄Alkyl-and halogen-substituted benzenediols, for example 3-bromo-5-tert-butyl-phenyl-1, 2-diol, 3, 6-dichloro-4-methyl-phenyl-1, 2-diol, 3-bromo-4, 5-dimethyl-phenyl-1, 2-diol or 3-chloro-4, 6-di-tert-butyl-phenyl-1, 2-diol, but are not limited thereto.

In one non-limiting embodiment, bisphenols and hydrogenated bisphenols that may be used to prepare the polylactone diols may be represented by the following formula:

wherein R is₁₃And R₁₄Are each independently selected from C₁-C₄One of alkyl, chloro or bromo; p and q are each independently an integer from 0 to 4; a-is selected from-O-, -S (O)₂)-、-C(O)-、-CH₂-、-CH＝CH-、-C(CH₃)₂-、-C(CH₃)(C₆H₅) -orOne of the divalent bonding groups in (a),represents a benzene ring or a cyclohexane ring. A non-limiting specific example of a bisphenol that can be used to prepare the polylactone diols is 4, 4' -isopropylidenediphenol. A non-limiting specific example of a hydrogenated bisphenol that can be used to prepare the polylactone diols is 4, 4' -isopropylidenebicyclohexanol.

In one non-limiting embodiment, the lactones that can be used to prepare the polylactone diols have from 3 to 8 carbon atoms in the cyclic lactone ring and can be represented by the formula,

wherein h is an integer selected from 1 to 6, e.g. 1, 2, 3, 4,5 or 6, R₂、R₃And R₄Each independently selected from hydrogen and C₁-C₁₂Alkyl of (C)₅-C₆Cycloalkyl of, C₁-C₆With the proviso that R is one of alkoxy, benzyl or phenyl₂、R₃And R₄At least h +2 of the total number of groups is hydrogen. In another non-limiting embodiment, each R₂、R₃And R₄Are each hydrogen。

Examples of lactones that can be used to prepare the polylactone diols include: beta-propiolactone; gamma-butyrolactone; beta-butyrolactone; delta-valerolactone; α -methyl- γ -butyrolactone; beta-methyl-gamma-butyrolactone; gamma valerolactone; beta 0-caprolactone; monomethyl-, monoethyl-, monopropyl-, monoisopropyl-, etc. to monododecyl-epsilon-caprolactone; methoxy and ethoxy epsilon-caprolactone; cyclohexyl epsilon-caprolactone; phenyl epsilon-caprolactone; benzyl epsilon-caprolactone; ζ heptalactone (enatholactone); and β 1 octalactone (caprylactone), but are not limited thereto. In one non-limiting embodiment of the invention, R₂、R₃And R₄Are each hydrogen, h is 4, and the lactone is epsilon-caprolactone.

In one non-limiting embodiment, the second copolymerizable monomer can be represented by the formula:

wherein m and n are each independently an integer from 0 to 6, the sum of m and n is from 0 to 6, R₉And R₁₀Each independently selected from hydrogen or methyl, R₁₁And R₁₂Each independently selected from hydrogen or C₁-C₂B is selected from the group consisting of linear or branched alkylene, phenylene, C₁-C₄Or a divalent bonding group of a group represented by the formula:

wherein R is₁₅And R₁₆Are each independently selected from C₁-C₄P and q are integers each independently selected from 0 to 4,represents a divalent phenyl group or a divalent cyclohexyl group whenWhen it is a divalent phenyl group, D is-O-, -S-, -S (O)₂)-、-C(O)-、-CH₂-、-CH＝CH-、-C(CH₃)₂-、-C(CH₃)(C₆H₅) -, orWhen in useWhen it is a divalent cyclohexyl group, D is-O-, -S-, -CH₂-or-C (CH)₃)₂-。

In one non-limiting embodiment, B is a divalent bonding group represented by the formula,

whereinRepresents a phenyl group.

In one non-limiting embodiment, R₉And R₁₀Are each methyl, R₁₁And R₁₂Each is hydrogen, p, q, r and s are each 0, D is-C (CH)₃)₂-, and the sum of m and n is selected from 0 to 4.

In one non-limiting embodiment, the third copolymerizable monomer can be represented by the formula:

wherein o and u are each independently selected from a positive number, the sum of o and u is from 7 to 70, R₉、R₁₀、R₁₁、R₁₂And B are as defined above.

In another non-limiting embodiment, the sum of o and u is from 10 to 30.

In one non-limiting embodiment, the fourth copolymerizable monomer can be represented by the formula:

wherein R is₅、R₈And R₁₁Is as defined above, d is a number selected from 0 to 20, and j is a number selected from 3 to 6.

In another non-limiting embodiment, d is 3 to 15, R₈The polyhydric alcohol derived therefrom is trimethylolpropane, pentaerythritol or dipentaerythritol. In a further non-limiting embodiment, d is from 5 to 10.

In one non-limiting embodiment, the fifth copolymerizable monomer may be the reaction product of a polycarbonate polyol chloroformate and a hydroxy (meth) acrylate. It can be prepared by a process comprising:

(a) preparing a chloroformate intermediate of a polyol containing carbonate group(s); and

(b) the chloroformate group of the chloroformate intermediate is reacted with a hydroxy (meth) acrylate.

The preparation of the chloroformate intermediate and the subsequent reaction with the hydroxy (meth) acrylate may be carried out by methods known in the art. As known to those skilled in the art, the reaction of chloroformate groups with hydroxy-functional (meth) acrylates is typically carried out in the presence of an acid scavenger, such as an alkali metal hydroxide, followed by washing and isolation of the final polyol ((meth) acrylycarbonate) monomer mixture. The molar equivalent ratio of hydroxy-functional (meth) acrylate to chloroformate groups in the chloroformate intermediate mixture in step (b) may be less than 1: 1, and in one non-limiting embodiment is at least 1: 1 (i.e., all chloroformate groups are reacted with hydroxy (meth) acrylate). In step (b) of the process, the molar equivalent ratio of hydroxy (meth) acrylate to chloroformate groups may be from 1: 1 to 1.5: 1.0, for example 1.1: 1.0.

In another non-limiting embodiment, the fifth copolymerizable monomer can also be prepared by a method comprising reacting the hydroxyl group of a polyol containing carbonate groups with a chloroformate-functional (meth) acrylate represented by the formula:

wherein X and R₅Respectively as defined previously in this application.

Chloroformate-functional (meth) acrylates represented by the above formula may be prepared by methods known to those skilled in the art. In one non-limiting embodiment, a hydroxy-functional (meth) acrylate, such as 2-hydroxyethyl (meth) acrylate, is reacted with phosgene in a molar ratio to produce a chloroformate-functional (meth) acrylate represented by the above formula.

In one non-limiting embodiment, the reaction of the hydroxyl groups of the polyol with the chloroformate groups of the chloroformate-functional (meth) acrylate is carried out in the presence of an acid scavenger, such as an alkali metal hydroxide, followed by washing and isolation of the final mixture of polyol ((meth) acrylylcarbonate) monomers (as known to those skilled in the art). The molar equivalent ratio of hydroxyl groups of the polyol mixture to chloroformate groups in the chloroformate-functional (meth) acrylate may be broadly distributed, and in one non-limiting embodiment, the molar equivalent ratio is selected to react all of the polyol mixtures with chloroformate-functional (meth) acrylate, i.e.: a molar equivalent ratio of less than or equal to 1: 1, for example from 0.5: 1 to 1: 1.

In another non-limiting embodiment, the fifth copolymerizable monomer can be prepared by reacting the polyol (in excess) with (meth) acryloyl chloride and washing and isolating the monofunctional methacrylate. This material is reacted with phosgene to form a chloroformate intermediate, and subsequently reacted with a polyol containing at least one carbonate group.

In one non-limiting embodiment, the sixth copolymerizable monomer can be prepared by reacting a polycarbonate polyol with (meth) acryloyl chloride (in excess) and washing and isolating the polycarbonate polyol (meth) acrylate.

In one non-limiting embodiment, the seventh copolymerizable monomer is a monoethylenically unsaturated monomer polymerizable by free radical initiation. The monoethylenically unsaturated monomer may be selected from alkyl (meth) acrylates, vinyl aromatic monomers, vinyl halides, vinylidene halides, vinyl esters, (meth) acryloxypropyltri (C)₁-C4) alkoxysilanes, (meth) acrylic acids or mixtures thereof.

In another non-limiting embodiment, the monoethylenically unsaturated monomer may be selected from stearyl methacrylate, methyl methacrylate, isobornyl methacrylate, phenoxyethyl methacrylate, cyclohexyl methacrylate, styrene, vinyl toluene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene fluoride, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl larerate, vinyl pyrrolidinol (pyrollidinorol), vinyl benzoate, acryloxypropyl trimethoxysilane (meth) acrylate, or mixtures thereof.

In one non-limiting embodiment, the eighth copolymerizable monomer is an allyl functional monomer having at least two allyl groups. The allyl-functional monomer may be used in the polymerizable composition at a level of no more than 5 weight percent, based on the total weight of the monomers. In another non-limiting embodiment, the allyl functional monomer is selected from the group consisting of:

(i) an allyl-functional monomer represented by the formula,

R₁₇-[-O-C(O)O-R₁₈]₂

wherein R is₁₇Is a divalent residue of a diol selected from 1, 2-ethanediol diethylene glycol or 1, 2-propanediol, R₁₈Is allyl;

(ii) an allyl-functional monomer represented by the formula:

wherein R is₁₅And R₁₆Are each independently selected from C₁-C₄One of alkyl, chlorine or bromine, p and q are integers each independently selected from 0 to 4, -A-is selected from-O-, -S (O)₂)-、-C(O)-、-CH₂-、-CH＝CH-、-C(CH₃)₂-、-C(CH₃)(C₆H₅) -orA divalent bonding group of (A), R₁₈Is allyl;

(iii) an allyl-functional monomer represented by the formula:

wherein R is₁₈Is allyl; or

(iv) (iv) a mixture of at least two selected from (i), (ii) and (iii).

In further non-limiting embodiments, the allyl functional monomer is selected from the group consisting of:

(i) polyether glycol bis (allyl carbonate);

(ii) polylactone diol bis (allyl carbonate); or

(iii) Mixtures thereof.

In one non-limiting embodiment, the invention is polymerizableThe polymerization of the composition may be carried out byHawley’s Condensed Chemical DictionaryThirteenth edition, 1997 John Wiley&The mechanism described in Sons page 901-902 "polymerization" proceeds. These mechanisms include "addition", in which a free radical is an initiator which reacts with the double bond of the monomer to produce a new free electron on one side of the monomer while adding to the other side of the monomer, and "condensation", which involves the condensation of two reacting monomers to produce a water molecule, and so-called "oxidative coupling" processes.

In a further non-limiting embodiment, polymerization of the polymerizable organic composition of the present invention can be accomplished by adding to the composition an initiating amount of a material capable of generating free radicals, such as an organic peroxide or an azobis (organonitrile) compound, i.e.: and (3) an initiator. Methods for polymerizing the polyol ((meth) acryloyl carbonate) monomer are well known to those skilled in the art, and any of these well known techniques may be used for the polymerization of the polymerizable organic composition described above. These polymerization methods include thermal polymerization, photopolymerization, or a combination of these methods.

Non-limiting examples of organic peroxides that can be used as thermal polymerization initiators include: peroxymonocarbonates, such as t-butyl peroxyisopropyl carbonate; peroxydicarbonates, such as di (2-ethylhexyl) peroxydicarbonate, di (sec-butyl) peroxydicarbonate and diisopropyl peroxydicarbonate; diacyl peroxides, such as 2, 4-dichlorobenzoyl peroxide, isobutyryl peroxide, decanoyl peroxide, lauroyl peroxide, propionyl peroxide, acetyl peroxide, benzoyl peroxide and p-chlorobenzoyl peroxide; peroxyesters such as t-butyl peroxypivalate, t-butyl peroxyoctanoate, and t-butyl peroxyisobutyrate; methyl ethyl ketone peroxide, and acetyl cyclohexylsulfonyl peroxide. The thermal initiators used in one non-limiting embodiment are those which do not discolor the final polymer.

Non-limiting examples of azobis (organonitrile) compounds that may be used as thermal polymerization initiators include: azobis (isobutyronitrile), azobis (2, 4-dimethylvaleronitrile), or mixtures thereof.

The amount of thermal polymerization initiator used to initiate and polymerize the polymerizable organic compositions of the present invention can vary depending on the particular initiator used and the photochromic article desired to be obtained, such as a molded lens, a coated lens, or an overmolded (over mold). It is desirable to use only the amount necessary to initiate and maintain the polymerization reaction. Namely: and (4) initiating amount. For peroxides, such as diisopropyl peroxydicarbonate used in one non-limiting embodiment, the initiator is generally used in an amount of 0.01 to 3.0 parts per 100 parts of the polymerizable organic composition (phm). In another non-limiting embodiment, 0.05 to 1.0phm is used to initiate the polymerization. The thermal curing process comprises heating the polymerizable organic composition in the presence of an initiator, in one non-limiting embodiment, at room temperature to 85-125 ℃ for 2-30 hours.

In one non-limiting embodiment, photopolymerization of the polymerizable organic composition according to the present invention can be carried out using ultraviolet light, visible light, or a combination of both in the presence of a photopolymerization initiator. Non-limiting examples of the photopolymerization initiator include: benzoin, benzoin methyl ether, benzoin isobutyl ether benzyl alcohol, acetophenone, 4' -dichlorobenzophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-isopropylthioxanthone and 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide.

The amount of photopolymerization initiator used to initiate and polymerize the polymerizable organic compositions of the present invention can vary depending on the particular initiator used and the desired photochromic article to be obtained. It is desirable to use only the amount necessary to initiate and maintain the polymerization reaction. Namely: and (4) initiating amount. In one non-limiting embodiment, the photopolymerization initiator is used in an amount of 0.01 to 5 wt%, based on the total weight of the monomer components.

In one non-limiting embodiment, the light source used for photopolymerization is selected from those capable of emitting ultraviolet light. The light source may be a mercury lamp, a germicidal lamp, or a xenon lamp. Visible light, such as sunlight, may also be used. The exposure time will vary depending on, for example, the wavelength and light intensity of the light source and the particular photochromic article, and is generally empirically determined.

In another non-limiting embodiment, various conventional additives may be added to the polymerizable organic compositions of the present invention. Such additives may include light stabilizers, heat stabilizers, antioxidants, ultraviolet light absorbers, mold release agents, fixed (non-photochromic) dyes, pigments, solvents and polymerization inhibitors to improve stability on storage, and ultraviolet light absorbers (as opposed to photochromic compounds). Anti-yellowing additives, such as 3-methyl-2-butenol, organic pyrocarbonates, and triphenyl phosphite [ CAS 101-02-0], may also be added to the polymerizable organic compositions of the present invention to improve yellowing resistance.

In a further non-limiting embodiment, it is also contemplated to add a polymerization moderator or a mixture of polymerization moderators to the polymerizable organic composition of the present invention to reduce the formation of distortions, such as striations, in the polymer resulting therefrom. Non-limiting examples of polymerization moderators include: dilauroyl thiodipropionate, terpinolene, 1-isopropyl-4-methyl-1, 4-cyclohexadiene, 1-isopropyl-4-methyl-1, 3-cyclohexadiene, 1, 3-diisopropenylbenzene, alpha-methylstyrene, 2, 4-diphenyl-4-methyl-1-pentene, 1-diphenylethylene, cis-1, 2-diphenylethylene, 2, 6-dimethyl-2, 4, 6-octatriene, 4-tert-butylcatechol, 3-methyl-2-butenol, or a mixture thereof.

In one non-limiting embodiment, the polymerization moderator is added to the polymerizable organic composition of the present invention in an amount of from 0.01 to 20 weight percent, for example, from 0.1 to 10 weight percent or from 0.3 to 5 weight percent, based on the total weight of the polymerizable organic composition. The amount of polymerization moderator can range between any combination of these values, within the ranges noted above, for example: 0.015-19.999 wt%.

In one non-limiting embodiment, the polymers polymerized from the polymerizable organic compositions of the present invention are solid and transparent or optically clear, and thus they can be used as optical elements, for example, optical lenses, such as planar and vision correction lenses and contact lenses, sunglass lenses, windows, automotive transparencies, such as windshields, T-roofs, side and rear windows, and for aircraft transparencies, among others. In another non-limiting embodiment, the thickness of the polymer can be 0.5 millimeters or more.

In another non-limiting embodiment, a two-part lens mold of glass is filled with a polymerizable composition that may additionally contain a catalytic amount of azobisisobutyronitrile. The glass mold was sealed and placed in an oven. The thermal polymerization process is initiated and the process is carried out at 40-110 ℃ for 10-20 hours. Thereafter, the mold is opened to take out the resulting lens, i.e.: a polymer. The polymer lens thus produced is then annealed for a period of time and at a temperature sufficient to relieve residual stresses in the lens. The temperature is typically 100-110 ℃ and the annealing is carried out for 1-5 hours. If the photochromic substance is not included in the polymerizable composition, it can be added to the polymer by imbibition, permeation, or other migration methods known in the art.

In a further non-limiting embodiment, a semi-finished single vision (SFSV) lens having an adherent cast layer of the photochromic polymerizable composition of the present invention can be prepared by an overmolding process. Typically, a predetermined volume of photochromic polymerizable composition is added to the volume defined by the spherical concave or negative (minus) glass mold, which volume matches the front surface curve and outer diameter of the SFSV lens. The glass mold was fitted with an annular polyvinyl chloride liner that extended about 0.2 mm above the mold and had an inside diameter that was less than about 4 mm of the outside diameter of the mold. After monomer addition, the SFSV lens is carefully placed on top of the added polymerizable composition, which diffuses to fill the above defined volume. An annular glass plate having an outer diameter equal to or larger than that of the lens is disposed on the rear surface of the lens. A spring clip is positioned so that one side of the clip is on the front surface of the female mold and the other side of the clip is on the back surface of the glass sheet. The resulting assembly was wound around and sealed to the plate-lens-gasket-mold with polyurethane tape. The assembly was preheated in an air oven at 30-95 ℃ for 60 minutes, after which the temperature was raised to 95-125 ℃ and lowered to 82 ℃ over 3 hours. A wedge is inserted under the spacer between the lens and the mold to separate the assemblies. The lens now has an adherent casting of 150 and 180 microns.

When the polymer of the present invention is used as a matrix for a photochromic compound, for example, as a photochromic article such as a photochromic lens, in one non-limiting embodiment, the polymer should be transparent to activate the portion of the electromagnetic spectrum of the photochromic substance in the matrix, for example, the wavelength of ultraviolet light (UV) that causes the photochromic substance to produce color or be in a ring-opened form, and the portion of the visible spectrum that includes the maximum wavelength of the photochromic substance that absorbs in a UV activated state, for example, in a ring-opened form.

In various non-limiting embodiments, the polymerizable composition of the present invention can be prepared by injecting it into a mold and polymerizing it by a process such as that known in the art as in situ molding. Polymers, such as lenses, prepared by cast polymerization (in the absence of a photochromic amount of an organic photochromic substance) of the polymerizable compositions of the present invention can be used to make photochromic articles by applying or incorporating photochromic compounds into the polymer using methods known in the art. Such non-limiting art-known methods include: (a) dissolving or dispersing the photochromic substance in the polymer, for example, by immersing the polymer in a hot solution of the photochromic substance or by imbibing the photochromic substance into the polymer by thermomigration; (b) providing a photochromic substance as a barrier layer between adjacent layers of polymer, e.g., as part of a polymer film, and (c) using the photochromic substance as part of a coating disposed on the surface of the polymer. The term "imbibe" or "imbibe" means the mere penetration of photochromic substances into the polymer, imbibing photochromic substances in the polymer with solvent-assisted migration, vapor phase migration, and other similar migration mechanisms.

Non-limiting examples of photochromic compounds that can be used with the polymerizable compositions of the present invention are organic photochromic compounds having a desired chromatic color. They typically have at least one activated absorption peak in the range of about 400-700 nm. They may be used alone or in combination with photochromic compounds that complement their activated color.

In one non-limiting embodiment, the organic photochromic substance includes chromenes such as naphthopyrans, benzopyrans, indolopyrans, and phenanthropyrans; spiropyrans, such as spiro (benzindoline) naphthopyrans, spiro (indoline) benzopyrans, spiro (indoline) naphthopyrans, spiro (indoline) quinropyrans and spiro (indoline) pyrans; oxazines, such as spiro (indoline) phenoxazines, spiro (indoline) pyridobenzoxazines, spiro (indoline) phenoxazines and spiro (indoline) benzoxazines; mercury salts of dithizone, fulgides, fulgimides, and mixtures of these photochromic compounds. These photochromic compounds are described in U.S. Pat. Nos. 5,645,767, 6,153,126 and US6,296,785B1 at column 30, line 44 to column 31, line 5.

In another non-limiting embodiment, the photochromic compounds described herein are used in photochromic amounts and in proportions (when mixtures are used) such that the coating composition to which they are applied or to which they are added exhibits the desired final color, for example, a substantially neutral color when activated with unfiltered sunlight, such as gray or brown, i.e.: the activated photochromic compound is given a color as close to neutral as possible. Neutral gray and neutral brown are preferred; however, other popular colors may also be used. Further discussion regarding neutral color and ways to describe color can be found in U.S. Pat. No. 5,645,767 at column 12, line 66 to column 13, line 19.

The term "photochromic amount" as used in the present specification and claims refers to an amount of a photochromic compound or substance that is at least sufficient to produce a photochromic effect discernible to the naked eye upon activation. In other words, the photochromic amount for an absorbed substance is the "photochromically effective amount" of the photochromic substance that is at least partially absorbed. The specific amount used will generally depend on the intensity of color desired under illumination. In one non-limiting embodiment, the more photochromic substance in the polymerizable composition of the present invention, or the more photochromic substance incorporated into the polymer of the present invention, the higher the color intensity of the final photochromic article.

In one non-limiting embodiment, the amount of photochromic material incorporated into the polymerizable composition ranges from 0.01 to 40 weight percent, based on the weight of the polymerizable composition. For example, the concentration of photochromic substance ranges from 0.05 to 30 weight percent, 0.1 to 20 weight percent, or 0.2 to 15 weight percent, such as 7 to 14 weight percent, based on the weight of the polymerizable composition. The concentration of the photochromic substance may range from any combination of these values within the above ranges, for example, from 0.05 to 39.95 wt%.

In one non-limiting embodiment, when photochromic substances are incorporated into the optically clear polymers of the present invention, such as by absorption, the amount of photochromic substance applied to the surface of the optically clear polymer is in the range of 0.01 to 2.00 milligrams per square centimeter of surface area of the polymer, such as 0.1 to 1.0 milligrams per square centimeter of surface area of the polymer. The concentration of the photochromic substance can range between any combination of these values within the ranges described above, for example, 0.015 to 1.999 milligrams per square centimeter of polymer surface area.

In one non-limiting embodiment, for medical or fashion reasons, compatible shades (both chemically and in color), i.e.; dyes, added to the polymerizable composition or applied to the polymer, to achieve better aesthetics. The particular dye selected will vary depending on the needs and results to be achieved. In one non-limiting embodiment, the dye may be selected to complement the color obtained by the activated photochromic substance, for example, to a more neutral color or to absorb a particular wavelength of incident light. In another non-limiting embodiment, a dye can be selected to provide a desired shade to the polymer when the photochromic substance is in the inactivated state.

In various non-limiting embodiments, the auxiliary material is added before, simultaneously with, or after the photochromic substance is applied or added to the polymerizable composition or cured polymer, or the auxiliary material may be added to the polymerizable composition in which the photochromic substance is used. For example, the ultraviolet light absorber and photochromic substance can be mixed before they are incorporated into the composition, or the absorbers can be laminated, e.g., laminated, as a layer between the photochromic polymer and the incident light. In addition, the stabilizer may be mixed with the photochromic substance before it is added to the composition to improve the resistance of the photochromic substance to optical fatigue. Stabilizers such as Hindered Amine Light Stabilizers (HALS), asymmetric diaryloxyamide (oxanilide) compounds, and single oxygen quenchers, such as nickel ions coordinated with organic ligands, polyphenol antioxidants, or mixtures thereof, are also contemplated. They may be used alone or in combination. These stabilizers are described in US4,720,356, US5,391,327 and US5,770,115.

The polymerizable compositions of the present invention may further comprise additional conventional ingredients which either impart desired properties to the composition or are required in the process of applying and curing the composition or which enhance the cured polymer therefrom. These components may be used in amounts up to 20% by weight, based on the weight of the monomers. For example, plasticizers can be used to adjust the fisher microhardness (microhardness) and/or photochromic properties of the photochromic polymerizable composition. Other such additional ingredients include rheology control agents, leveling agents such as surfactants, initiators, cure inhibitors, free radical scavengers, cross-linking agents, and adhesion promoters.

Non-limiting examples of adhesion promoters that may be used are organofunctional trialkoxysilanes having alkoxy substituents of 1 to 4 carbon atoms and polymerizable organofunctional silanes applied using the methods disclosed in U.S. Pat. No. 6,150,430 at column 2, line 39 to column 8, line 38. These include, but are not limited to, gamma-glycidoxypropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, 3, 4-epoxycyclohexylethyltrimethoxysilane, aminoethyltrimethoxysilane, or mixtures thereof. An amount of adhesion promoter may be used to improve adhesion of subsequently applied coatings to the overmould of the polymer or polymerizable composition of the invention to the lens blank. The adhesion promoter in an adhesion improving amount is an amount that exhibits improved adhesion when the adhesion is measured by ASTM D-3359-Standard test method using tape test B when compared to the polymer without the adhesion promoter.

The use of protective coatings, some of which may contain silicone polymers, as primers to improve adhesion of subsequently applied coatings has been described in U.S. Pat. No. 6,150,430. In one non-limiting embodiment, a non-staining coating is used. Non-limiting examples of commercially available coating products include SILVUE^®124 and HI-GARD^®Coatings, available from SDC coatings and PPG industries, respectively. Additionally, in one non-limiting embodiment, depending on the use of the article, it may be necessary to use a suitable protective coating on the exposed surface of the polymer, namely: a rub resistant coating and/or as an oxygen barrier coating to prevent scratches due to rubbing and abrasion and the interaction of oxygen with the photochromic compound, respectively. In some cases, the base layer and the protective coating are interchangeable, i.e.: the same coating can be used as both the primer and the protective coating. Non-limiting examples of hard coatings include those based on, for example, silicaInorganic materials such as titanium oxide and/or zirconium oxide, and ultraviolet-curable organic hard coatings.

In additional non-limiting embodiments, other coatings or surface treatments, such as tintable coatings, antireflective surfaces, and the like, may also be used on the articles of the present invention, i.e., the photochromic polymers. Antireflective coatings, such as single or multiple layers of metal oxides, metal fluorides, or other such materials, can also be deposited onto photochromic articles of the present invention, such as lenses, by vacuum evaporation, sputtering, or other methods.

One contemplated non-limiting embodiment is the use of the photochromic polymerizable compositions of the present invention to produce optically clear polymers, namely: materials suitable for optical applications, such as optical elements, e.g. flat and vision correction lenses and contact lenses, windows, transparent polymer films, automotive transparencies, e.g. windshields, aircraft transparencies, plastic sheeting, and the like. The refractive index of these optically transparent polymers may be from 1.48 to 2.00, for example from 1.495 to 1.75, especially from 1.50 to 1.66.

Another contemplated non-limiting embodiment, if necessary, is the use of the photochromic polymers of the present invention in combination with a suitable protective coating, such as silicone, to make photochromic optical articles.

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

Examples 1-14 were prepared using components 1, 2, and 3 and the photochromic component along with various methacrylate monomers. Example 15 describes the preparation and determination of photochromic lenses prepared in each example and the results of the determination according to the test of the accelerated weathering photochromic optical fatigue percentage.

Component 1

The reaction products of the isocyanates and polycarbonate polyols were prepared using the components listed in table 1.

TABLE 1
		Components	Weight (gram)
Starting materials 1
		PC-1122(a)THF(b)MEHQ(c)	936.10500.000.20
Raw material 2
		ICEMA(d)THF	155.16500.00

(a) An aliphatic polycarbonate diol, used is polyhexamethylene dicarbonate, available from Stahl, USA.

(b) Tetrahydrofuran (THF)

(c) Hydroquinone monomethyl ether

(d) Isocyanatoethyl methacrylate

Feed 1 was charged to an all-glass reactor. The components were mixed using an air distributor. The feed in the reactor was heated until the temperature of the feed reached 60 ℃. Feed 2 was added over about an hour. After the addition of starting material 2 was complete, the reaction mixture was mixed for 6 hours. The final solution was vacuum stripped at 40 ℃ for 1 hour at 10mm Hg. The final polymer solution obtained had a total solids content, determined on a total solution weight basis, of about 91.71 wt%. The weight average molecular weight of the polymer was about 6473 and the number average molecular weight was 2480 as determined by gel permeation chromatography using polystyrene as a standard.

Component 2

Step 1

The polylactone diol bis (chloroformate) intermediates were prepared from the components listed in table 2. The polycaprolactone diol bis (chloroformate) intermediate is used to prepare polycaprolactone diol bis ((meth) acryloyl carbonate) monomer.

TABLE 2
		Components	Weight (gram)
Starting materials 1
		Carbonyl chloride	67
Raw material 2
		Polylactone diol (e)	3993
Raw material 3
		Carbonyl chloride	1713

(e) TONE 0201 poly (. epsilon. -caprolactone) diol, available from Union Carbide.

Feed 1 was charged to a 5 liter four-necked round-bottomed jacketed flask over a period of 15 minutes with recirculating cooling to 5 ℃. The flask was equipped with an electric teflon polymer stirring paddle, a phosgene addition tube, a thermocouple, a pressure equalization addition funnel, and a condenser connected to a sodium hydroxide scrubber. After the addition of feed 1 was complete, feed 2 and feed 3 were added simultaneously to the flask over 8.5 hours and 7.5 hours, respectively. During the addition of feeds 2 and 3, the temperature of the observed flask contents did not exceed 38 ℃. After the addition of feed 2 was complete, a heating mantle was placed on the flask and the temperature of the contents of the flask was maintained at 32 ℃ for the remainder of the addition of feed 3. After the addition of feed 3 was complete, the contents of the flask were sparged with nitrogen at 32 ℃ for about 24 hours. The contents of the flask were transferred to a suitable container. The assay of the reaction was determined to be 99 wt% by titration of the product mixture and pyridine.

Step 2

The polylactonediol bis ((meth) acrylylcarbonate) monomer was prepared as follows along with the polylactonediol bis (chloroformate) intermediate of step 1 using the components listed in Table 3.

TABLE 3
			Components	Weight (gram)
Starting materials 1
			Polycaprolactone bis (chloroformate) intermediate hydroxyethyl methacrylate dichloromethane	328134200
Raw material 2
			50% sodium hydroxide (f)		102

(f) An aqueous solution containing 50 wt% of sodium hydroxide, based on the total weight of the solution.

Charge 1 was charged to a 1-liter round-bottomed jacketed glass flask. The flask was equipped with an electric teflon polymer stirring blade, a water condenser, a circulation cooling device (jacket for the flask), and a thermometer connected to a temperature feedback control device. The contents of the flask were cooled to 0 ℃ and feed 2 was added slowly over 35 minutes. During the addition of feed 2, the temperature of the observed flask contents did not exceed 20 ℃. After the end of feed 2 addition, 50 grams of water was added and the contents of the flask were stirred for an additional 2 hours at a temperature of about 20 ℃. 800 milliliters (ml) of deionized water and 0.05 grams of butylated hydroxytoluene were added to the flask and the contents of the flask were separated into an organic phase and an aqueous phase. The organic phase was collected and washed with 300 g of 10 wt% aqueous sodium hydroxide solution. 400 g of deionized water were added and the organic phase was collected after 1 hour. The organic phase was washed with 500 g of deionized water containing 0.035 g of butylated hydroxytoluene. After 1 hour the organic phase was collected and washed with 600 grams of deionized water. After 18 hours the organic phase was collected and sprayed with air for 2 hours. The organic phase was stripped at 35 ℃ for 30 minutes under 12mm Hg vacuum and at 48 ℃ for 40 minutes under 10mm Hg vacuum. The final product was filtered through a 0.45 micron filter. The yield of the final reactive oligomer product of component 2 was 85%, the hydroxyl value was 5.62mg KOH/g sample, and the weight average molecular weight of the polymer was 500-1400 as determined by gel chromatography using polystyrene as a standard.

Component 3

The reaction product of a polycarbonate polyol with (meth) acryloyl chloride was prepared from the components listed in table 4.

TABLE 4
		Components	Weight (gram)
Starting materials 1
		PC-1122(a) THF (b) MEHQ (c) sodium acetate	234.40301.300.2437.40
Raw material 2
		Methacryloyl chloride THF	26.2100.80

(e) An aliphatic polycarbonate diol, used is polyhexamethylene dicarbonate, available from Stahl, USA.

(f) Tetrahydrofuran (THF)

(g) Hydroquinone monomethyl ether

Feed 1 was fed into an all-glass reactor which had been purged with nitrogen. The reactor was placed in an ice bath and feed 2 was added over 1 hour while maintaining the reaction mixture temperature below 25 ℃. After the addition of starting material 2 was complete, the reaction mixture was warmed to room temperature over 95 minutes. The feed in the reactor was heated until the temperature of the feed reached 35 ℃. An aliquot of the reaction was quenched with methanol and analyzed by gas chromatography for methyl methacrylate to determine the reaction conversion. The complete reaction was diluted 1: 1 in ethyl acetate and washed twice with saturated sodium bicarbonate and brine, respectively. The resulting organic solution was dried over magnesium sulfate, filtered and concentrated to about 92% solids. The final material was used without further purification.

The amount of methyl methacrylate present was determined by co-injection of standards on a Hewelett Packard5890 series 2 gas chromatograph containing a Supelco SPB-8 capillary column. The retention time was measured to be 4.29 minutes under the following settings: the injection port temperature was 200 deg.C, the detection port temperature was 250 deg.C, the column temperature program was maintained at 40 deg.C for 2 minutes, the ramp at 40-220 deg.C @15 deg.C/min, and at 22 minutes @220 deg.C.

The data of the gel permeation chromatography show the following with respect to the obtained product: number average molecular weight was 2400, and weight average molecular weight was 5600. The GPC system was calibrated with polyethylene glycol standards.

Photochromic component

The photochromic components were prepared by adding each of the materials listed in Table 5 to a suitable container equipped with stirring and heating means. The final mixture was stirred and slowly heated to give a clear solution.

TABLE 5
		Material	Weight percent
NMP (g) photochromic #2(h) photochromic #3(i) photochromic #4(j) photochromic #5(k) Irganox 245(l) Tinuvin622(m)	15.0002.6250.6750.9003.3003.0002.000

The weight percentages listed in table 5 are based on the total weight of the monomers.

(g) N-methyl pyrrolidone

(h) 2H-naphtho [1, 2-b ] pyrans exhibiting a grayish blue color when irradiated with ultraviolet light.

(i) 2H-naphtho [1, 2-b ] pyrans exhibiting a blue-green color when irradiated with ultraviolet light.

(j) 2H-naphtho [1, 2-b ] pyrans exhibiting an orange-yellow color when irradiated with ultraviolet light.

(k) 2H-naphtho [1, 2-b ] pyrans exhibiting an orange-yellow color when irradiated with ultraviolet light.

(l) An antioxidant/stabilizer, available from Ciba Specialty Chemicals corp.

(m) a hindered amine ultraviolet light stabilizer, available from Ciba Specialty Chemicals Corp.

Examples 1 to 14

The monomers in weight percent for examples 1-14 are listed in table 6. The examples were prepared by the following steps: the monomer compositions listed in Table 6 were charged into a suitable vessel equipped with a stirring device and stirred for 1 hour after the following additions: 0.15 wt% of FC-431 fluorocarbon surfactant available from 3M and 28.0 wt% of the photochromic component of Table 5 were added, both weight percentages being based on the total weight of the monomers.

TABLE 6

Example #	1	2	3	4	5	6	7	8	9	10	11	12	13	14
															BPA2EO DMA(n)	45	40	30	45	45	45	70	70	70	70	70	70	70	70
Component 1	35	40	30	8.75	17.5	26.25	30	15	0	15	10	0	0	0
															Component 2	0	0	0	26.25	17.5	8.75	0	15	30	0	10	0	0	0
Component 3	0	0	0	0	0	0	0	0	0	15	10	0	0	0
															TMPTMA(o)	20	20	20	20	20	20	0	0	0	0	0	0	0	0
BPA 10EO DMA(p)	0	0	20	0	0	0	0	0	0	0	0	30	0	0
															BPA 20EO DMA(q)	0	0	0	0	0	0	0	0	0	0	0	0	30	0
BPA 30EO DMA(r)	0	0	0	0	0	0	0	0	0	0	0	0	0	30

(n) bisphenol A ethoxylated (1 EO/phenyl) dimethacrylate available from Sartomer, Inc

(o) trimethylolpropane trimethacrylate, available from Sartomer, Inc

(p) bisphenol A ethoxylated (5 EO/phenyl) dimethacrylate available from Sartomer, Inc

(q) bisphenol A ethoxylated (10 EO/phenyl) dimethacrylate available from Sartomer, Inc

(r) bisphenol A ethoxylated (15 EO/phenyl) dimethacrylate available from Sartomer, Inc

Example 15

Accelerated aging photochromic percent optical fatigue test (AWPPPF test) involves preparing lenses in parts a-C, coating the lenses with a polymerizable composition in part D, measuring the fischer microhardness of the coated lenses in part E, and determining photochromic performance and fatigue in part F, either before or after aging in part G.

The polymerizable compositions of the present invention were added to the coating compositions of examples 1-8, 10 and 11. Other polymerizable compositions not containing the polymerizable composition of the present invention, such as the compositions of examples 9, 12, 13 and 14, were also tested. The photochromic performance and fatigue measurements of coatings having comparable fischer microhardness levels were compared to determine if there was an increase or decrease in these parameters. Since the performance of photochromic compounds is generally known to be accelerated in softer polymer matrices, the physical properties of the coatings should be considered when comparing coated lenses having comparable fischer microhardness levels.

Part A

Use of CR-39 available from PPG Industries, Inc^®A series of flat lens blanks made of monomer. The lens blank diameter was 70 mm. All lens blanks were rinsed with dishwasher detergent (Lemon scientific joy) and water, soaked for 10 seconds in a 12.5 wt% aqueous sodium hydroxide solution at 60 c, based on the total weight of the solution, washed with deionized water, sprayed with isopropanol and dried.

Part B

The lenses prepared in part a were coated with an adhesion promoter composition described in U.S. patent No. 6,150,430. The adhesion promoter composition was applied to the surface of the lens by rotating the lens at 1500 revolutions per minute (rpm) while coating with the composition for 9 seconds.

Part C

All coated lenses in part B were cured by exposure to uv radiation. The lenses were irradiated for 10 seconds at 6 inches under a Dymax 5000EC point cure system rated at 400 watts per inch. After curing of the coated composition, each lens was cleaned with isopropanol at 1500rpm rotation for 9 seconds and dried before further processing.

Moiety D

Rotating the lens at 1500rpm and coating the time listed in Table 7 with the coating compositionAlternatively, the photochromic coating composition of table 6 was applied to the lens in part C to produce a coating having a thickness of about 30 microns after curing.

TABLE 7
		Example #	Rotating time (seconds)
123456789101112 and 1314	18.025.017.018.012.010.035.020.011.033.022.09.09.5

The coated lenses were cured by exposure to ultraviolet light exposure by exposing them to the path of a conveyor belt at a speed of 2.3 feet per minute (70.1cm per minute) under two 10 inch (25.4cm) long ultraviolet linear "V" lamps. The first lamp was held 2.5 inches (6.4cm) above the conveyor and the second lamp was 6.5 inches (16.5cm) above the conveyor. The cured system was obtained from a small-pore UV system (Eye Ultraviolet system) and inertized with nitrogen to a level of less than 100 parts per ml of oxygen.

Part E

The coated photochromic lenses prepared in section D were tested for microhardness using a Fischer HCV H-100 model observer available from Fischer Technology, Inc. The newtons per mm of the lenses coated in the examples were measured under the following conditions²Microscopic intensity of the meter: at 100 millinewton load, 30 load steps with 0.5 second pause between steps. The results listed in Table 8 were measured at an indenter depth of 2 μm.

TABLE 8
		Example No. 2	Micro hardness Newton per mm2
1234567891011121314	100868411711210512712714410810818913799

The results in Table 8 show that examples 1 to 8, 10 and 11 containing component 1 have microhardness of 84 to 108N/mm²Within the range of (1). Other examples have microhardness of 99-189N/mm²Within the range of (1).

Part F

The coated photochromic lenses prepared in part D were tested for photochromic response on an optical bench manufactured by Essilor of France, hereinafter referred to as "BMP". The coated photochromic lenses were exposed to 365nm uv light at about 14cm from the lamp for about 10 minutes to activate the photochromic compounds prior to testing on BMP. The UVA irradiance of the samples was measured to be 22.2 watts per square meter using a spectroradiometer type Licor Li-1800. The sample was then placed under a halogen lamp for about 10 minutes at about 36cm from the lamp to fade or deactivate the photochromic compounds in the sample. The brightness of the sample was measured by a Licor spectroradiometer to be 21.9 Klux. The lenses tested were then stored in a dark environment for at least 1 hour prior to testing on BMP.

The BMP consists of a flat metal surface on which two 150 watt xenon arc lamps (one lamp providing UV/VIS light efficacy and one lamp providing visible light additional efficacy) are mounted, placed 90 ° apart. The somewhat parallel output beams from the xenon arc lamps were combined and directed onto the sample cell and passed through an 50/50 beam splitter to an irradiance detector. Each lamp was independently filtered and shielded prior to entering the sample chamber and also shielded after mixing. Each lamp was also filtered with a Schott 3mm KG-2 pass-band filter. The lamp for supplementing the visible light is additionally filtered with a 400nm cutoff filter.

With the equipment, namely: software provided by bmpsofft version 2.1e may be used to control time, irradiance, air cell and sample temperature, grating, filter selection, and response determination. The software program for adjusting within the set range limits an optical feedback unit which, in turn, makes slight adjustments to the lamp wattage and subsequently the lamp output. If a selected irradiance cannot be achieved within the limits of the optical feedback unit, the program will indicate that a change in the selection of the neutral intensity filter for each lamp circuit is required.

Creating BMP software requires correlation factors between spectroradiometric measurements of the samples and the use of a graceby model 5380 two-way optometer fitted with a model #268UVA detector and a model #268P visible light detector. The vision detector is arranged on the optical steel rail carrier and receives half of the split and combined light beams from the xenon arc lamp. The lens sample chamber was held in place with a quartz window and self-centering sample holder. The cell temperature was controlled by software at 73.4F (23 ℃ C.) using a modified facility, ModelFX-10 environmental simulator. The irradiance of the samples was set at 6.7 watts UVA per square meter and 50Klux brightness. Response and color were measured using a zeiss model MCS 501 spectrophotometer with fiber optic cable optically transmitted from a tungsten halogen lamp and through the sample. The conditioned monitoring beam of the fiber optic cable, as it passes through the sample, is directed into a receiving fiber optic cable connected to a spectrophotometer while remaining perpendicular to the test sample. The optimal location for placing the sample in the sample chamber is where the activated xenon arc beam and the monitoring beam intersect to form two concentrated apertures. The incident angle of the xenon arc light beam to the sample placement point was approximately 20 ° in the vertical direction.

The response measurement is determined by recording the original unactivated transmittance, turning on the grating of the xenon lamp and measuring the transmittance through activation over a selected time interval, as a function of the change in light intensity (Δ OD) from the unactivated or faded state to the activated or dark state. The change in light intensity is determined according to the following equation: Δ OD is log (% Tb/% Ta), where% Tb is the percent transmission in the faded state and% Ta is the percent transmission in the activated state, with the base of the logarithm being 10.

Fading rate (T)^1/2) Is the time interval seconds taken for the activated state Δ OD of the photochromic compound in the test zone to reach half the maximum Δ OD after the activating light source is removed. Activation Rate (A)^1/2) Is the number of seconds of the time interval of irradiation taken to reach half the change in light intensity (Δ OD) obtained after 15 minutes of irradiation. The results of the photochromic coated lenses are listed in table 9.

TABLE 9

Example #	Δ OD at 15 min	A1/2(second)	T1/2(second)
				1234567891011121314	0.620.630.610.610.620.590.590.630.660.580.590.610.660.66	1816172120292225281720793323	64596386767087108117617551315191

The results in Table 9 show that component 1 alone or together with component 1 and component 2, component 3, trimethylolpropane trimethacrylate and/or with a bisphenol A (2 ethoxy ethers)Radical unit) dimethacrylate formulation bisphenol A (10 ethoxy units) dimethacrylate examples 1-8, 10 and 11 activation rates (A)^1/2) And/or fade rate (T)^1/2) Greater than all the examples tested except example 14. The light intensity change (Δ OD) of examples 1-8, 10 and 11 was comparable to or reduced from that of the other examples tested.

Examination of tables 8 and 9 shows that the Fischer microstrength of the coatings of examples 1, 4-8, 10 and 11 is equal to or greater than example 14, indicating the photochromic properties, such as the activation rate (A), exhibited by examples 1, 4-8, 10 and 11^1/2) And/or fade rate (T)^1/2) Is not due to the physical properties of the coating, such as being softer or having a lower fisher microstrength.

Moiety G

An ATLAS Ci4000 aging apparatus was used to simulate accelerated aging by solar irradiation. The results for the samples listed in table 10 were obtained after exposure to a filtered xenon lamp at an output of 0.25 watts per square meter at 340nM in an ATLAS Ci4000 weatherometer for 65 hours. The temperature in the ageing instrument was maintained at 45 ℃ and the relative humidity was controlled at 75%. The temperature of the lenses on the dark plate carrier does not typically exceed 55 ℃. After the lens has undergone the fatigue process, it is prepared and measured on the optical bench under the same conditions before exposure.

The fatigue percentage (% Fat) was determined by measuring the difference between the change in light intensity (Δ OD) of the test sample before and after accelerated aging and calculating the percentage reduction in light intensity represented by the difference. The light intensity change (Δ OD) was determined by the following method: a test lens in the faded state is inserted into the sample carrier and the transmission (T) is measured_B) Turning on the grating from the xenon lamp provides simulated solar illumination to convert the test sample from a faded state to an activated (i.e.: dark) state, measuring the activated state transmittance (T)_A) And calculating the light intensity change according to: Δ OD ═ log (T)_B/T_A) (base of logarithm is 10). The results may differ by ± 2.

The percent light fatigue was measured for wavelengths passed through the filter and was substantially consistent with the visible response observed by the human eye. The results are shown in Table 10.

Watch 10

Example No. 2	% degree of light fatigue
		7891011121314	1822263027282624

The results in Table 10 show that example 7, which contains 30 wt% of component 1, has a lower percentage of light fatigue than all other test samples. Example 8, containing 15 wt% of component 1 and 2 respectively, showed an average of the light fatigue percentages of examples 7 and 9, and example 9, containing 30 wt% of component 1 and 30 wt% of component 2 respectively. Example 10, which contained 15 wt% component 1 and 15 wt% component 3, where component 3 is a polycarbonate polyol-based dimethacrylate reaction product different from component 1, exhibited a higher percentage of light fatigue than all other samples tested. The percent light fatigue results for example 11, which contained 10 wt% of components 1, 2 and 3, respectively, were between examples 9 and 10.

Examples 12, 13 and 14 show that the percent photosensibility decreases with increasing ethoxy units from 10 to 20 to 30 units, respectively.

The tests in tables 9 and 10 show that the use of component 1 alone or in combination with component 2 and/or component 3 formulated in (meth) acrylates in place of bisphenol a dimethacrylate having 10, 20 or 30 ethoxy units unexpectedly results in photochromic lenses with improved properties, e.g., faster activation and fade rates, and/or reduced fatigue, such as extended life.

The present invention has been described with reference to specific details of particular embodiments, which should not be construed as limitations on the scope of the invention except insofar as and to the extent that they are included in the accompanying claims.

Claims (32)

1. A polymerizable composition comprising a photochromic amount of at least one photochromic compound, at least one material comprising at least one carbonate group and at least one hydroxyl group, and at least one monoisocyanate containing material having at least one unsaturated group, said polymerizable composition being adapted to provide a reduction in the percent fatigue of the photochromic compound in the accelerated weathering photochromic percent optical fatigue test when at least partially cured.

2. The polymerizable composition of claim 1 wherein the at least one photochromic compound is selected from chromenes, spiropyrans, oxazines, mercury dithizonates, fulgides, fulgimides, or mixtures thereof.

3. The polymerizable composition of claim 1 wherein the at least one unsaturated group is selected from allyl, acrylic and/or methacrylic, vinyl, or mixtures thereof.

4. The polymerizable composition of claim 3 wherein the at least one unsaturated group is acrylic and/or methacrylic.

5. The polymerizable composition of claim 1 wherein the at least one material comprising at least one carbonate group and at least one hydroxyl group is a polycarbonate polyol.

6. The polymerizable composition of claim 1, further comprising at least one other copolymerizable monomer.

7. The polymerizable composition of claim 6 wherein the at least one other copolymerizable monomer is an acrylic and/or methacrylic monomer.

8. A polymerizable composition comprising:

(a) the reaction product of a polyol containing at least one carbonate group and an isocyanate containing one reactive isocyanate group and at least one polymerizable double bond;

(b) a photochromic amount of at least one photochromic compound.

9. The polymerizable composition of claim 8, further comprising (c) at least one other monomer copolymerizable with component (a).

10. The polymerizable composition of claim 8 wherein the reaction product (a) is represented by the formula:

wherein R' is a polyol residue containing at least one carbonate group, R₅Is hydrogen or methyl, E is-NH-; x is a residue selected from the group consisting of a linear or branched alkylene group, a linear or branched polyoxyalkylene group, a cyclic alkylene group, a phenylene group, a polyhydric alcohol and C₁-C₄A divalent bonding group of the alkyl-substituted phenylene group of (a); i is selected from an integer of 2 to 6.

11. The polymerizable composition of claim 8 wherein the isocyanate of (a) is selected from the group consisting of:

(a) an isocyanate represented by the formula:

CH₂＝C(R₅)-C(O)OX-N＝C＝O

wherein R is₅Is hydrogen or methyl, X is a divalent linking group selected from the group consisting of linear or branched alkylene, linear or branched polyoxyalkylene, cyclic alkylene, phenylene, the residue of a polyol or C₁-C₄Alkyl-substituted phenylene groups of (a);

(b) m-isopropenyl-alpha, alpha-dimethylbenzyl isocyanate;

(c) the reaction product of at least one acrylic functional monomer containing one vinyl ether group with isocyanic acid; or

(d) Mixtures thereof.

12. Polymerizable composition according to claim 11, characterized in that the isocyanate is selected from isocyanatoethyl methacrylate; m-isopropenyl-alpha, alpha-dimethylbenzyl isocyanate; 1- (2-methacryloyloxyethoxy) ethyl isocyanate, or mixtures thereof.

13. The polymerizable composition of claim 8 wherein the polyol containing at least one carbonate group is a polycarbonate polyol represented by the formula:

wherein R is₆And R₇Each independently selected from divalent straight or branched chain alkylene, cyclic alkylene or divalent C₆-C₁₅Aryl, a is an integer selected from 1 to 20.

14. The polymerizable composition of claim 13 wherein the polycarbonate polyol is the reaction product of at least one bis (chloroformate) and at least one polyol.

15. The polymerizable composition of claim 14 wherein the bis (chloroformate) is monoethylene glycol bis (chloroformate), diethylene glycol bis (chloroformate), propylene glycol bis (chloroformate), butanediol bis (chloroformate), hexanediol bis (chloroformate), neopentyl glycol bis (chloroformate), bisphenol a bis (chloroformate), or a mixture thereof.

16. The polymerizable composition of claim 14 wherein the polyol is bisphenol a; trimethylolethane; trimethylolpropane; di (trimethylolpropane) dimethylolpropionic acid; ethylene glycol; propylene glycol; 1, 3-propanediol; 2, 2-dimethyl-1, 3-propanediol; 1, 2-butanediol; 1, 4-butanediol; 1, 3-butanediol; 1, 5-pentanediol, 2, 4-pentanediol; 2, 2, 4-trimethyl-1, 3-pentanediol; 2-methyl-1, 3-pentanediol; 2-methyl-1, 5-pentanediol; 3-methyl-1, 5-pentanediol; 1, 6-hexanediol; 2, 5-hexanediol; 2-ethyl-1, 3-hexanediol; 1, 4-cyclohexanediol; 1, 7-heptanediol; 2, 4-heptanediol; 1, 8-octanediol; 1, 9-nonanediol; 1, 10-decanediol; 2, 2-dimethyl-3-hydroxypropyl-2, 2-dimethyl-3-hydroxypropionate; diethylene glycol; triethylene glycol; tetraethylene glycol; polyethylene glycol; dipropylene glycol; tripropylene glycol; polypropylene glycol; 1, 4-cyclohexanedimethanol; 1, 2-bis (hydroxymethyl) cyclohexane; 1, 2-bis (hydroxyethyl) cyclohexane; alkoxylation products of 1 mole of 2, 2-bis (4-hydroxyphenyl) propane (i.e., bisphenol A) with 2 to 10 moles of ethylene oxide, propylene oxide or mixtures thereof; poly (oxybutylene) glycol or mixtures thereof.

17. The polymerizable composition of claim 9 wherein the amount of (a) is at least 5 wt% to less than 95 wt% based on the total weight of non-photochromic monomers in the composition.

18. The polymerizable composition of claim 8 wherein the reaction product (a) is a monomer having a number average molecular weight greater than 2000.

19. The polymerizable composition of claim 9 wherein the at least one other copolymerizable monomer is selected from the group consisting of:

(a) a radically polymerizable monomer represented by the following formula:

wherein R is₈Being a polyvalent residue of a polyol, R₅Is hydrogen or methyl, i is an integer from 2 to 6, X is a divalent linking group selected from the group consisting of linear or branched alkylene, linear or branched polyoxyalkylene, cyclic alkylene, phenylene, the residue of a polyol or C₁-C₄Alkyl-substituted phenylene groups of (a);

(b) a radically polymerizable monomer represented by the following formula:

wherein m and n are integers independently selected from 0 to 6, the sum of m and n is 0 to 6, R₉And R₁₀Each independently selected from hydrogen or methyl, R₁₁And R₁₂Each independently selected from hydrogen or C₁-C₂B is selected from the group consisting of linear or branched alkylene, phenylene, C₁-C₄Or a divalent bonding group of a group represented by the formula:

wherein R is₁₅And R₁₆Are each independently selected from C₁-C₄P and q are integers each independently selected from 0 to 4,represents a divalent phenyl group or a divalent cyclohexyl group whenWhen it is a divalent phenyl group, D is-O-, -S-, -S (O)₂)-、-C(O)-、-CH₂-、-CH＝CH-、-C(CH₃)₂-、-C(CH₃)(C₆H₅) -, orWhen in useWhen it is a divalent cyclohexyl group, D is-O-, -S-, -CH₂-or-C (CH)₃)₂-；

(c) A free radically polymerizable monomer represented by the formula:

wherein o and u are each independently selected from a positive number, the sum of o and u is from 7 to 70, R₉、R₁₀、R₁₁、R₁₂And B is as defined above;

(d) a radically polymerizable monomer represented by the following formula:

wherein R is₅、R₈And R₁₁D is an integer selected from 0 to 20, j is an integer selected from 3 to 6;

(e) the reaction product of a polycarbonate polyol chloroformate with a hydroxy acrylate and/or a hydroxy methacrylate;

(f) reaction products of polycarbonate polyols with acryloyl chloride and/or methacryloyl chloride;

(g) monoethylenically unsaturated, free-radically polymerizable monomers;

(h) a free radically polymerizable allyl-functional monomer having at least two allyl groups, with the proviso that the allyl-functional monomer is used in an amount of not more than 5 weight percent based on the total weight of the monomers; or

(i) Mixtures of the above monomers.

20. The polymerizable composition of claim 19, wherein:

(a)R₈is a polyvalent residue of a polyol selected from aliphatic polyols, cycloaliphatic polyols, aromatic polyols or polyols containing ester groups containing at least 2 hydroxyl groups, i is 2, X is a linear or branched alkylene group;

(b)R₉and R₁₀Are each methyl, R₁₁And R₁₂Each is hydrogen, p, q, r and s are each 0, D is-C (CH)₃)₂The sum of m and n is 0 to 4;

(c) the sum of o and u is 10 to 30;

(d)R₈is the residue of trimethylolpropane, pentaerythritol or dipentaerythritol and d is 3 to 15;

(e) a reaction product of a polycarbonate polyol chloroformate;

(f) a reaction product of a polycarbonate polyol and methacryloyl chloride;

(g) the monoethylenically unsaturated monomer is alkyl acrylate and/or alkyl methacrylate, vinyl aromatic monomer, vinyl halide, vinylidene halide, vinyl ester, acryloxypropyltri (C)₁-C₄) Alkoxysilane and/or methacryloxypropyl tris (C)₁-C₄) Alkoxysilanes, acrylic acids and/or formazanAcrylic acid or mixtures thereof;

(h) the allyl functional monomer is:

(i) an allyl-functional monomer represented by the formula,

R₁₇-[-O-C(O)O-R₁₈]₂

wherein R is₁₇Is a divalent residue of a diol selected from 1, 2-ethanediol diethylene glycol or 1, 2-propanediol, R₁₈Is allyl;

(ii) an allyl-functional monomer represented by the formula,

wherein R is₁₅And R₁₆Are each independently selected from C₁-C₄One of alkyl, chlorine or bromine, p and q are integers each independently selected from 0 to 4, -A-is selected from-O-, -S (O)₂)-、-C(O)-、-CH₂-、-CH＝CH-、-C(CH₃)₂-、-C(CH₃)(C₆H₅) -orA divalent bonding group of (A), R₁₈Is allyl;

(iii) an allyl-functional monomer represented by the formula,

wherein R is₁₈Is allyl; or

(iv) A mixture of at least two selected from (i), (ii), and (iii).

21. The polymerizable composition of claim 19 wherein R in (a) is₈Is the residue of a polyol represented by the formula:

R¹-(Y-(C(O)(-CR²R³)_h-CHR⁴-O)_t-H)_y

wherein: y is-O-or-NR-, R is hydrogen or C₁-C₁₂An alkyl group; r₁Being an initiator-derived organic radical, R₂、R₃And R₄Each independently selected from hydrogen and C₁-C₁₂Alkyl of (C)₅-C₆Cycloalkyl of, C₁-C₆With the proviso that R is one of alkoxy, benzyl or phenyl₂、R₃And R₄At least h +2 of the total number is hydrogen and the letter h is an integer selected from 1 to 6; t is an integer selected from 1 to 100; y is an integer selected from 2 to 6.

22. The polymerizable composition of claim 19 wherein R in (a) is₈Is the residue of the reaction product of at least one diol and at least one lactone; the diol is a linear or branched aliphatic diol having 2-20 carbon atoms, poly (C)₂-C₄) Alkylene glycols, cycloaliphatic diols having 5 to 8 carbon atoms in the ring, monocyclic aromatic diols, bisphenols, hydrogenated bisphenols, or mixtures thereof; the lactone is as follows: beta-propiolactone; gamma-butyrolactone; beta-butyrolactone; delta-valerolactone; α -methyl- γ -butyrolactone; beta-methyl-gamma-butyrolactone; gamma valerolactone; beta 0-caprolactone; monomethyl-beta 1-caprolactone; monoethyl-beta 2-caprolactone; monopropyl-beta 3-caprolactone; monododecyl-beta 4-caprolactone; methoxy epsilon-caprolactone; ethoxy epsilon-caprolactone; cyclohexyl epsilon-caprolactone; phenyl epsilon-caprolactone; benzyl epsilon-caprolactone; ζ -heptalactone; beta 5-octalactone or a mixture thereof.

23. An at least partially cured photochromic polymerizate of a composition comprising photochromic amounts of at least one photochromic compound, at least one material comprising at least one carbonate group and at least one hydroxyl group, and at least one monoisocyanate containing material having at least one unsaturated group, wherein said at least partially cured photochromic polymerizate is adapted to have a reduced percent fatigue of the photochromic compound in an accelerated weathering photochromic percent optical fatigue test.

24. An at least partially cured photochromic polymerizate of a composition according to claim 23 wherein the composition further comprises at least one other copolymerizable monomer.

25. An at least partially cured photochromic polymerizate of a composition according to claim 24 wherein said at least one other copolymerizable monomer is an acrylic and/or methacrylic monomer.

26. An at least partially cured photochromic polymerizate of a composition comprising the following components:

a) the reaction product of a polyol containing at least one carbonate group and an isocyanate containing one reactive isocyanate group and at least one polymerizable double bond;

b) a photochromic amount of at least one photochromic compound.

27. An at least partially cured photochromic polymerizate of a composition according to claim 26 wherein the composition further comprises (c) at least one other monomer copolymerizable with component (a).

28. An at least partially cured photochromic polymerizate of a composition according to claim 27 wherein the at least one other copolymerizable monomer is an acrylic and/or methacrylic monomer.

29. An at least partially cured photochromic polymerizate of a composition according to claim 26 wherein the polymerizate is an optical element.

30. A photochromic article comprising an at least partially cured polymerizate of a composition comprising at least one material comprising at least one carbonate group and at least one hydroxyl group and at least one monoisocyanate containing material having at least one unsaturated group, said polymerizate having an effective photochromic amount of at least one partially absorbed photochromic material, said photochromic article being adapted to provide a reduction in the percent fatigue of the photochromic compound in the accelerated weathering photochromic percent optical fatigue test.

31. A photochromic article comprising an at least partially cured polymerized product of a composition comprising the product of reacting a polyol containing at least one carbonate group with an isocyanate containing one reactive isocyanate group and at least one polymerizable double bond, said polymer having a photochromic effective amount of at least one partially absorbed photochromic material.

32. The photochromic article of claim 31 wherein the at least partially cured polymerizate of one composition further comprises at least one other copolymerizable monomer.